CN103396296A - 2,6-dimethyl-6-methoxy heptanol series derivatives and preparation method thereof - Google Patents
2,6-dimethyl-6-methoxy heptanol series derivatives and preparation method thereof Download PDFInfo
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Abstract
The invention discloses 2,6-dimethyl-6-methoxy heptanol series derivatives and a preparation method thereof. A structural formula of the 2,6-dimethyl-6-methoxy heptanol series derivatives is shown in a figure (shown in the specification), wherein R is ethyl, propyl, isopropyl, butyl, isobutyl, isoamyl, cyclopentyl, hexyl, cyclohexyl or allyl. The preparation method is shown as follows: methyl heptenone is used as a raw material, the methyl heptenone reacts with methanol under the catalysis of concentrated sulfuric acid to obtain 6-methyl-6-methoxy-2-heptanone, epoxy carboxylate is obtained by a condensation reaction of the 6-methyl-6-methoxy-2-heptanone and ethyl chloroacetate under the effects of a strong alkali, then 2,6-dimethyl-6-methoxy heptaldehyde is obtained by saponification and an acidifying decarboxylation reaction, the 2,6-dimethyl-6-methoxy heptanol series derivatives are obtained by a series of addition reactions of the 2,6-dimethyl-6-methoxy heptaldehyde and a bromoalkane Grignard reagent, and the 2,6-dimethyl-6-methoxy heptanol series derivatives have different fragrances and are new perfume compounds by identification.
Description
Technical field
The present invention relates to a kind of spices, particularly a kind of 2,6-dimethyl-6-methoxyl group enanthol series derivates and preparation method thereof.
Background technology
United States Patent (USP) (US 4287133) has introduced Sulcatone and the method (see figure 1) that the Darzens condensation reaction prepares melonal occurs ethyl acetate under the sodium alkoxide effect, this melonal is the spices with strong new fresh muskmelon delicate fragrance, can be used as flavouring agent and use, be mainly used in preparing muskmelon, cucumber and tropical fruit type essence.But aldehydes is unstable, uses inconvenient.
Summary of the invention
One of purpose of the present invention is unstable in order to solve above-mentioned melonal spices, use the technical problem such as inconvenient and provide a kind of 2,6-dimethyl-6-methoxyl group enanthol series derivates, it has melon perfume (or spice), the fragrance of a flower, fruital, glue perfume (or spice), metal perfume (or spice), the pleasant fragrance such as ocean breath, and its stable performance, have characteristics easy to use as spices.
Two of purpose of the present invention is to provide above-mentioned a kind of 2, the preparation method of 6-dimethyl-6-methoxyl group enanthol series derivates.
Technical scheme of the present invention
A kind of 2,6-dimethyl-6-methoxyl group enanthol series derivates, as shown in Figure 2, wherein R is ethyl, propyl group, sec.-propyl, butyl, isobutyl-, isopentyl, cyclopentyl, hexyl, cyclohexyl or allyl group to its structural formula;
R is ethyl, and 2,6-dimethyl-6-methoxyl group enanthol series derivates has rubber fragrance and light fruital;
When R was propyl group, 2,6-dimethyl-6-methoxyl group enanthol series derivates had the fragrant and ripe melon perfume of glue fragrance;
When R was sec.-propyl, 2,6-dimethyl-6-methoxyl group enanthol series derivates had the fragrant fragrance of glue perfume (or spice), the banksia rose and melon;
When R was butyl or isobutyl-, 2,6-dimethyl-6-methoxyl group enanthol series derivates had the fragrant fragrance of well-done melon;
When R was isopentyl, 2,6-dimethyl-6-methoxyl group enanthol series derivates had elegant melon perfume and simple and elegant sea wind breath;
When R was cyclopentyl, 2,6-dimethyl-6-methoxyl group enanthol series derivates had strong metal fragrance and light delicate fragrance;
When R was hexyl, 2,6-dimethyl-6-methoxyl group enanthol series derivates had graceful delicate fragrance, fruital and strong ocean breath;
When R was cyclohexyl, 2,6-dimethyl-6-methoxyl group enanthol series derivates had the fragrant fragrance of graceful delicate fragrance, fruital, ocean breath and melon;
When R was allyl group, 2,6-dimethyl-6-methoxyl group enanthol series derivates had pleasant melon perfume and simple and elegant fragrance of a flower fragrance.
Above-mentioned a kind of 2, the preparation method of 6-dimethyl-6-methoxyl group enanthol series derivates, namely take Sulcatone as raw material, under sulphuric acid catalysis and the methyl alcohol reaction generate 6-methyl-6-methoxyl group-2-heptanone;
Condensation reaction under the highly basic effect generates the epoxy carboxylicesters to the 6-methyl of gained-6-methoxyl group-2-heptanone with ethyl chloroacetate again, more successively through saponification, the acidifying decarboxylic reaction, obtain 2,6-dimethyl-6-methoxyl group enanthaldehyde;
2 of gained, 6-dimethyl-6-methoxyl group enanthaldehyde obtain 2,6-dimethyl-6-methoxyl group enanthol series derivates with corresponding alkyl magnesium bromide through a series of addition reactions again.
Above-mentioned a kind of 2, the preparation method of 6-dimethyl-6-methoxyl group enanthol series derivates, specifically comprise the steps:
(1), alkylated reaction
Sulcatone and methyl alcohol are thrown in reaction flask, slowly added the vitriol oil, Sulcatone and methyl alcohol reaction generate 6-methyl-6-methoxyl group-2-heptanone under the catalysis of the vitriol oil;
Above-mentioned reaction process is controlled temperature 50-60 ℃, and the time is 18-28h;
Above-mentioned Sulcatone used, the amount of methyl alcohol and the vitriol oil is calculated in mass ratio, i.e. Sulcatone: methyl alcohol: and the vitriol oil is 100:250:13;
(2), Darzens condensation reaction
The 6-methyl of step (1) gained-6-methoxyl group-2-heptanone and ethyl chloroacetate are thrown in reaction flask, slowly added sodium alkoxide, under the effect of sodium alkoxide, 6-methyl-6-methoxyl group-2-heptanone and ethyl chloroacetate generation condensation reaction generate the epoxy carboxylicesters;
It is-10～-15 ℃ that above-mentioned condensation reaction is controlled temperature, and the time is 3～6h;
Above-mentioned condensation reaction 6-methyl used-6-methoxyl group-2-heptanone, ethyl chloroacetate and sodium alkoxide calculate in molar ratio, i.e. 6-methyl-6-methoxyl group-2-heptanone: ethyl chloroacetate: sodium alkoxide is 1:1.25:1.4;
After above-mentioned condensation reaction finishes, be down under room temperature the methanol solution that adds 2.25 molar equivalent sodium hydroxide and carry out saponification reaction, the saponification reaction process control temp is 50 ℃, time is 2～4h, and after saponification fully, 20KPa reclaims methyl alcohol, treat no longer to go out cut, be incorporated as the frozen water of raw material 6-methyl-3～5 times of amounts of 6-methoxyl group-2-heptanone, stir the 10min left and right, stratification;
Remove the upper strata organic layer, lower floor's methyl tertiary butyl ether extracting twice, remove the organic layer that extracts gained for twice, merges the water layer of twice extraction gained;
By the water layer after above-mentioned merging with mass percent concentration be 35% concentrated hydrochloric acid regulate pH be after 5～6 again with methyl tertiary butyl ether extraction three times, merges the organic layer that extracts gained for three times;
75～85 ℃ of organic layer normal pressures after above-mentioned merging are reclaimed to solvent, in the gained enriched material, be incorporated as again the copper powder of its weight 1%, be heated to 150～180 ℃ carry out decomposition reaction 2～5h after, control the 10KPa underpressure distillation, collect 62～66 ℃ of cuts and namely obtain 2,6-dimethyl-6-methoxyl group enanthaldehyde;
(3), 2, the addition reaction of 6-dimethyl-6-methoxyl group enanthaldehyde and Grignard reagent
the magnesium sheet of oven dry is joined in flask, use the tetrahydrofuran (THF) submergence, add 1～2 bromoalkane, 1 iodine, after adding thermal booster reaction, control drop rate and be 0.4～0.8ml/min and drip the mixed solution that the tetrahydrofuran (THF) by bromoalkane and 5～8 times of its weight forms, dropwise and react again the 1h left and right, in bathing, cryosel is cooled to-5～0 ℃, and then the control drop rate is that 0.4～0.8ml/min drips by 2 of step (2) gained, the mixed solution that 6-dimethyl-6-methoxyl group enanthaldehyde and tetrahydrofuran (THF) form, after dropwising, move to room temperature, the GC trace analysis, to 2, when 6-dimethyl-6-methoxyl group enanthaldehyde GC content was almost constant, reaction finished, slowly add the ammonium chloride solution cancellation, layering, water layer methyl tertiary butyl ether extracting twice, merge organic layer, organic layer is washed once with deionized water, then separate organic layer, to obtain organic layer under normal pressure 80-120 ℃ distill, except desolventizing, the residuum of gained carries out the column chromatography purification with the pillar of 30cm*3.5cmi.d, obtain 2, 6-dimethyl-6-methoxyl group enanthol series derivates,
Above-mentioned 2, in the mixed solution that 6-dimethyl-6-methoxyl group enanthaldehyde and tetrahydrofuran (THF) form, the amount of 2,6-dimethyl-6-methoxyl group enanthaldehyde and tetrahydrofuran (THF), by 2,6-dimethyl-6-methoxyl group enanthaldehyde: tetrahydrofuran (THF) is the ratio of 1mol:1000g;
Magnesium wherein, bromoalkane, the mol ratio of 2,6-dimethyl-6-methoxyl group enanthaldehyde: 1.3～1.6:1.2～1.5:1;
Described bromoalkane is monobromethane, N-PROPYLE BROMIDE, bromine isopropyl alkane, n-butyl bromide, bromine Trimethylmethane, bromine iso-pentane, bromohexane, bromocyclopentane, bromocyclohexane or allyl bromide 98;
In above-mentioned addition reaction process, when described bromoalkane was bromocyclopentane or bromocyclohexane, when itself and 2,6-dimethyl-6-methoxyl group enanthaldehyde reacted, addition reaction, mainly occurred at-40 ℃～-78 ℃ in the main linked reaction that occurs in cryosel is bathed;
When described bromoalkane is allyl bromide 98, when itself and 2,6-dimethyl-6-methoxyl group enanthaldehyde reacted, feed way was slightly different, after namely first using 5% allyl bromide 98 initiation reaction, then 15% allyl bromide 98 being dissolved in to 8～10 times of tetrahydrofuran (THF)s slowly drips, 0.5 after～1h dropwises, maintain the temperature at 10～20 ℃, get 2,6-dimethyl-6-methoxyl group enanthaldehyde is with after 80% allyl bromide 98 and 5～8 times of tetrahydrofuran (THF)s mix, 2～3h adds, and at this temperature, stirs 1h, and the GC trace analysis finishes to reaction.
2 of above-mentioned gained, 6-dimethyl-6-methoxyl group enanthol series derivates, comment perfume (or spice) by the perfumer, determines that its fragrance is different, has melon perfume (or spice), the fragrance of a flower, fruital, glue perfume (or spice), metal perfume (or spice), the pleasant fragrance such as ocean breath, be therefore a kind of novel fragrance compounds.
Useful achievement of the present invention
Of the present invention 2,6-dimethyl-6-methoxyl group enanthol series derivates, be the series of new flavor compounds, has melon perfume (or spice), the fragrance of a flower, and fruital, glue perfume (or spice), metal perfume (or spice), the pleasant fragrance such as ocean breath, and stable chemical nature, can be used as spices and develop.
The accompanying drawing explanation
The synthetic route of Fig. 1, United States Patent (USP) (US4287133) watermelon aldehyde;
Fig. 2, a kind of 2, the structural formula of 6-dimethyl-6-methoxyl group enanthol series derivates;
The building-up reactions schematic diagram of Fig. 3, intermediate product 6-methyl-6-methoxyl group-2-heptanone;
Fig. 4, intermediate product 2, the building-up reactions schematic diagram of 6-dimethyl-6-methoxyl group enanthaldehyde;
Fig. 5,2, the synthetic reaction process schematic diagram of 6-dimethyl-6-methoxyl group enanthol series derivates.
Embodiment
Below by specific embodiment, also by reference to the accompanying drawings the present invention is further set forth, but do not limit the present invention.
A kind of 2,6-dimethyl-6-methoxyl group enanthol series derivates, as shown in Figure 2, wherein R is ethyl, propyl group, sec.-propyl, butyl, isobutyl-, isopentyl, cyclopentyl, hexyl, cyclohexyl or allyl group to its structural formula;
R is ethyl, and 2,6-dimethyl-6-methoxyl group enanthol series derivates has rubber fragrance and light fruital;
When R was propyl group, 2,6-dimethyl-6-methoxyl group enanthol series derivates had the fragrant and ripe melon perfume of glue fragrance;
When R was sec.-propyl, 2,6-dimethyl-6-methoxyl group enanthol series derivates had the fragrant fragrance of glue perfume (or spice), the banksia rose and melon;
When R was butyl or isobutyl-, 2,6-dimethyl-6-methoxyl group enanthol series derivates had the fragrant fragrance of well-done melon;
When R was isopentyl, 2,6-dimethyl-6-methoxyl group enanthol series derivates had elegant melon perfume and simple and elegant sea wind breath;
When R was cyclopentyl, 2,6-dimethyl-6-methoxyl group enanthol series derivates had strong metal fragrance and light delicate fragrance;
When R was hexyl, 2,6-dimethyl-6-methoxyl group enanthol series derivates had graceful delicate fragrance, fruital and strong ocean breath;
When R was cyclohexyl, 2,6-dimethyl-6-methoxyl group enanthol series derivates had the fragrant fragrance of graceful delicate fragrance, fruital, ocean breath and melon;
When R was allyl group, 2,6-dimethyl-6-methoxyl group enanthol series derivates had pleasant melon perfume and simple and elegant fragrance of a flower fragrance.
Above-mentioned a kind of 2, the preparation method of 6-dimethyl-6-methoxyl group enanthol series derivates, namely take Sulcatone as raw material, under sulphuric acid catalysis and the methyl alcohol reaction generate 6-methyl-6-methoxyl group-2-heptanone, its reaction process schematic diagram is as shown in Figure 3;
Condensation reaction under the highly basic effect generates the epoxy carboxylicesters to the 6-methyl of gained-6-methoxyl group-2-heptanone with ethyl chloroacetate again, then, successively through saponification, acidifying decarboxylic reaction, obtains 2,6-dimethyl-6-methoxyl group enanthaldehyde, and its reaction process schematic diagram as shown in Figure 4;
2 of gained, 6-dimethyl-6-methoxyl group enanthaldehyde obtains 2 with corresponding alkyl magnesium bromide through a series of addition reactions again, 6-dimethyl-6-methoxyl group enanthol series derivates, as shown in Figure 5, bromoalkane and dry magnesium rod react and obtain the alkyl magnesium bromide its reaction process schematic diagram in anhydrous THF, then with 2,6-dimethyl-6-methoxyl group enanthaldehyde reacts at low temperatures, use the ammonium chloride cancellation, obtain 2,6-dimethyl-6-methoxyl group enanthol series derivates.
The pillar of the 30cm*3.5cmi.d that the present invention is used (purchased from Shanghai He Qi Instrument Ltd.).
Embodiment 1
A kind of 2,6-dimethyl-6-methoxyl group enanthol series derivates, wherein R is ethyl.
Above-mentioned a kind of 2, the preparation method of 6-dimethyl-6-methoxyl group enanthol series derivates, specifically comprise the steps:
(1), alkylated reaction
In the 2000mL four-hole boiling flask, add Sulcatone 440 grams, methyl alcohol 1100 grams, add 95% the vitriol oil 65 grams under stirring, be heated to 50 ℃, backflow 22h, GC analyzes, and reactant transforms 83.5%, add sodium carbonate 70.4 grams, neutralisation of sulphuric acid, reclaim methyl alcohol, add 500g water dissolution inorganics, system layering, separatory, water layer adds methyl tertiary butyl ether (150ml*3) extraction, merges organic layer, underpressure distillation, obtain product 6-methyl-6-methoxyl group-2-heptanone 319.3 grams, productive rate 58%, GC content 91.2%;
(2), Darzens condensation reaction
get 0.2mol(31.6g) 6-methyl-6-methoxyl group-2-heptanone and 0.25mol (30.6g) ethyl chloroacetate be in the 250mL there-necked flask, under-10 ℃-15 ℃, slowly add the sodium methylate powder, 2h adds, insulated and stirred 2h, slowly rise to room temperature, by 0.45mol(18.0g) NaOH is dissolved in 150mL methyl alcohol and slowly drips, drip saponification 3h, reclaim under reduced pressure methyl alcohol, then in reaction flask, add 150mL water, stir, layering, organic layer water (50mL*2) extraction, combining water layer, layering after the acidifying of water layer use 35.4g concentrated hydrochloric acid, water layer extracts with methyl tertiary butyl ether (120mL*3), merge organic layer, the organic layer saturated NaCl solution washing of 100mL, separatory, survey organic layer and be slightly acidic, methyl tertiary butyl ether is removed in decompression, in organic enriched material, add the 0.3g copper powder, be heated to 150 ℃, extremely without bubble formation, be down to room temperature, underpressure distillation, obtain 11g 2, 6-dimethyl-6-methoxyl group enanthaldehyde,
(3), 2, the addition reaction of 6-dimethyl-6-methoxyl group enanthaldehyde and ethylmagnesium bromide
0.0165mol(0.4g by oven dry) magnesium sheet joins in flask, use the tetrahydrofuran (THF) submergence, add 1～2 monobromethane, 1 iodine, after adding thermal booster reaction, will be by 0.015mol(1.6g) monobromethane is dissolved in mixed solution that the 15g tetrahydrofuran (THF) obtains to control drop rate is that 0.4～0.8ml/min is added drop-wise to wherein, dropwise and react again the 1h left and right, it is cooling in cryosel is bathed, again will be by the 0.01mol(1.7g of step (2) gained) 2, 6-dimethyl-6-methoxyl group enanthaldehyde be dissolved in the 10g tetrahydrofuran (THF), obtain 2, 6-dimethyl-6-methoxyl group enanthaldehyde solution adds wherein take drop rate as 0.4～0.8ml/min, after dropwising, move to room temperature, the GC trace analysis, to reacting 6-methoxyl group 2 used, after when 6-dimethyl enanthaldehyde GC content was almost constant, reaction finished, slowly add 10% ammonium chloride solution 10mL cancellation reaction, layering, water layer methyl tertiary butyl ether extracting twice, merge organic layer, wash with water once, separate organic layer, to obtain organic layer under normal pressure 80-120 ℃ distill, except desolventizing, residuum carries out column chromatographic isolation and purification with the pillar of 30cm*3.5cmi.d, obtain the 1-ethyl-2 of GC content 97.3%, 6-dimethyl-6-methoxyl group enanthol,
Magnesium wherein, monobromethane, the mol ratio of 2,6-dimethyl-6-methoxyl group enanthaldehyde is 1.3～1.6:1.2～1.5:1;
The final product of above-mentioned gained passes through IR, HNMR, and the CNMR analyzing and testing, its analytical results is as follows:
IR：894w，1072s，1249s，1402s，2902w，2972s，3668s。
1H-NMR(CDCl3)：0.86(2d，J=6.5，11.5，3H)；0.93(t，J=6.5，3H)；1.12(s，6H)；1.15-1.20(m，9H)；1.76(s，1H)；3.15(s，3H)；3.25-3.5(m，1H)。
13C-NMR(CDCl3)：76.49；74.60；48.99；40.13；37.79/38.51；33.90/32.37；27.24/26.28；24.95；24.95；21.59/21.46；13.41/15.38；10.64/10.32。
By above-mentioned analytical results, can be drawn, the final product of above-mentioned gained is 1-ethyl-2,6-dimethyl-6-methoxyl group enanthol.
The 1-ethyl-2 of above-mentioned gained, 6-dimethyl-6-methoxyl group enanthol is commented perfume (or spice) through the perfumer, determines that it has rubber fragrance and light fruital.When above-mentioned a kind of 2, when in the preparation method's of 6-dimethyl-6-methoxyl group enanthol series derivates step (3), monobromethane used substitutes with N-PROPYLE BROMIDE, bromine isopropyl alkane, n-butyl bromide, bromine Trimethylmethane, bromine iso-pentane or bromohexane, finally obtaining R is 2 of propyl group, sec.-propyl, butyl, isobutyl-, isopentyl or hexyl, 6-dimethyl-6-methoxyl group enanthol series derivates.
By IR, HNMR, the CNMR analyzing and testing has also obtained checking.Concrete the result is as follows:
When final product is 1-propyl group-2, during 6-dimethyl-6-methoxyl group enanthol, IR, HNMR, CNMR analyzing and testing result is as follows:
IR：888w，1064s，1230s，1404s，2895w，2973s，3675s。
1H-NMR(CDCl3)：0.87-0.9(2d，J=7，12.5，3H)；0.94(t，J=7，3H)；1.14(s，6H)；1.2-1.60(m，12H)；3.18(s，3H)；3.40-3.55(m，1H)。
13C-NMR(CDCl3)：74.49/75.69；74.59；49.03；40.17；38.21/38.86；36.70/35.68；33.86/32.40；24.97；24.97；21.63/21.51；19.42/19.23；14.11/15.31；13.57。
When final product is 1-sec.-propyl-2, during 6-dimethyl-6-methoxyl group enanthol, IR, HNMR, CNMR analyzing and testing result is as follows:
IR：879w，1064s，1239s，1375s，1463s，2925w，2973s，3666s。
1H-NMR(CDCl3)：0.75-1.0(m，10H)；1.12(s，6H)；1.15-1.85(m，9H)；3.00-3.10(m，1H)；3.15(s，3H)。
13C-NMR(CDCl3)：79.99/81.03；74.57；48.99；40.15；35.00/35.83；34.73/31.69；30.93/30.93；24.93；24.90；21.43/21.30；19.39/20.00；18.56；12.96/16.35。
When final product is 1-butyl-2, during 6-dimethyl-6-methoxyl group enanthol, IR, HNMR, CNMR analyzing and testing result is as follows:
IR：645w，723w，869w，1054s，1230s，1385s，1463s，2896w，2984s，3676s。
1H-NMR(CDCl3)：0.82-0.89(d，J=7，3H)；0.89-0.94(t，J=7，3H)；1.15(s，6H)；1.18-1.73(m，15H)；3.15(s，3H)；3.35-3.55(m，1H)。
13C-NMR(CDCl3)：75.03/75.94；74.59；49.01；40.15；38.20/38.83；34.18/33.15；33.88/32.39；28.47/28.28；24.93；24.93；22.76；21.62/21.50；14.02/15.32；13.54。
When final product is 1-isobutyl--2, during 6-dimethyl-6-methoxyl group enanthol, IR, HNMR, CNMR analyzing and testing result is as follows:
IR：635w，733w，889w，1074s，1240s，1405s，1463s，2896w，2974s，3675s。
1H-NMR(CDCl3)：0.85-0.97(m，9H)；1.15(s，6H)；1.23-1.85(m，12H)；3.15(s，3H)；3.45-3.65(m，1H)。
13C-NMR(CDCl3)：74.60/73.68；72.90；48.99；43.66/42.49；40.14/；38.64/39.92；33.80/32.44；24.93/24.96；24.93/24.90；24.80/24.69；23.60/23.88；21.98/21.69；21.61/21.52；13.62/15.17。
When final product is 1-isopentyl-2, during 6-dimethyl-6-methoxyl group enanthol, IR, HNMR, CNMR analyzing and testing result is as follows:
IR：869w，1064s，1240s，1404s，2896w，2984s，3686。
1H-NMR(CDCl3)：0.84-0.92(m，9H)；1.13(s，6H)；1.15-1.58(m，13H)；1.65(s，1H)；3.18(s，3H)；3.42-3.55(m，1H)。
13C-NMR(CDCl3)：75.31/76.24；74.60；49.02；40.14；38.14/38.79；35.46/35.26；33.92；32.28/32.42；28.12/31.16；24.94/24.97；24.94/24.97；22.65/22.76；22.52/22.43；21.6/21.50；13.50/15.37。
When final product is 1-hexyl-2, during 6-dimethyl-6-methoxyl group enanthol, IR, HNMR, CNMR analyzing and testing result is as follows:
IR：723w，879w，1074s，1230s，1395s，1463s，2906w，2984s，3676s。
1H-NMR(CDCl3)：0.89-0.95(m，6H)；1.15(s，6H)；1.20-1.72(m，18H)；3.18(s，3H)；3.40-3.60(m，1H)。
13C-NMR(CDCl3)：75.03/76.00；74.60/74.48；49.05；40.15/40.00；38.21/38.83；34.52；33.89/33.49；31.84/32.39；29.39/29.67；26.24/26.05；24.95/24.87；24.95/24.84；22.61；21.63/21.52；14.04；13.56.minorisomer：40.48；39.38；36.73；36.64；19.48；18.47；15.34。
Embodiment 2
A kind of 2,6-dimethyl-6-methoxyl group enanthol series derivates, wherein R is cyclohexyl.
(1), alkylated reaction is with embodiment 1;
(2), the Darzens condensation reaction is with embodiment 1;
(3), 2, the addition reaction of 6-dimethyl-6-methoxyl group enanthaldehyde and cyclohexyl bromination magnesium
0.0165mol(0.4g by oven dry) magnesium sheet joins in flask, use the tetrahydrofuran (THF) submergence, add 1～2 bromocyclohexane, 1 iodine, after adding thermal booster reaction, will be by 0.015mol(2.5g) bromocyclohexane is dissolved in mixed solution that the 15g tetrahydrofuran (THF) obtains to control drop rate is that 0.4～0.8ml/min is added drop-wise to wherein, dropwise and react again the 1h left and right, in bathing, low-temp reaction is cooled to-40 ℃, again will be by the 0.01mol(1.7g of step (2) gained) 2, 6-dimethyl-6-methoxyl group enanthaldehyde be dissolved in the 10g tetrahydrofuran (THF), obtain 2, 6-dimethyl-6-methoxyl group enanthaldehyde solution adds wherein take drop rate as 0.4～0.8ml/min, after dropwising, move to room temperature, the GC trace analysis, to reacting used 2, when 6-dimethyl-6-methoxyl group enanthaldehyde GC content was almost constant, reaction finished, slowly add 10% ammonium chloride solution 10mL cancellation reaction, layering, water layer methyl tertiary butyl ether extracting twice, merge organic layer, wash with water once, separate organic layer, to obtain organic layer under normal pressure 80-120 ℃ distill, except desolventizing, residuum carries out column chromatographic isolation and purification with the pillar of 30cm*3.5cmi.d, obtain GC content and be 89.6% 1-cyclohexyl-2, 6-dimethyl-6-methoxyl group enanthol,
Magnesium wherein, bromoalkane, the mol ratio of 2,6-dimethyl-6-methoxyl group enanthaldehyde is 1.3～1.6:1.2～1.5:1.
The final product of above-mentioned gained passes through IR, HNMR, and the CNMR analyzing and testing, its analytical results is as follows:
IR：723w，889w，1064s，1240s，1414s，2896w，2974s，3676s。
1H-NMR(CDCl3)：0.80-0.93(2d，J=6.5，3H)；0.9-1.15(m，2H)；1.13(s，6H)；1.19-2.10(m，17H)；3.17(s，3H)；3.05-3.16(m，1H)。
13C-NMR(CDCl3)：78.94/80.62；74.62；49.04；40.74/40.27；40.14/40.21；34.75/35.02；34.72/31.33；29.43/30.15；29.14/27.24；26.48/26.54；26.24/26.19；26.04；24.96；24.92；21.51/21.36；12.84/16.51。
By above-mentioned analytical results, can be drawn, the final product of above-mentioned gained is 1-cyclohexyl-2,6-dimethyl-6-methoxyl group enanthol.
The 1-cyclohexyl-2 of above-mentioned gained, 6-dimethyl-6-methoxyl group enanthol is commented perfume (or spice) through the perfumer, determines that it has the fragrant fragrance of graceful delicate fragrance, fruital, ocean breath and melon.
When R is cyclopentyl, adopt and with the identical method of embodiment 2, can obtain 1-cyclopentyl-2,6-dimethyl-6-methoxyl group enanthol.
When final product is 1-cyclopentyl-2, during 6-dimethyl-6-methoxyl group enanthol, IR, HNMR, CNMR analyzing and testing result is as follows:
IR：626w，743w，879w，1074s，1230s，1395s，1453s，2876w，2964s，3471w，3666s。
1H-NMR(CDCl3)：0.84-0.98(2d，J=7，3H)；1.15(s，6H)；1.19-2.10(m，17H)；3.17(s，3H)；3.22-3.31(m，1H)。
13C-NMR(CDCl3)：79.18/80.33；74.60；49.03；43.93/43.24；40.14/40.29；36.40/37.10；34.94；29.93/30.85；29.17/29.36；25.52/25.61；25.43；24.96；24.94；21.62/21.58；12.70/16.86。
Embodiment 3
A kind of 2,6-dimethyl-6-methoxyl group enanthol series derivates, wherein R is allyl group.
(1), alkylated reaction is with embodiment 1;
(2), the Darzens condensation reaction is with embodiment 1;
(3), 2, the addition reaction of 6-dimethyl-6-methoxyl group enanthaldehyde and allyl group bromination magnesium
0.0165mol(0.4g by oven dry) magnesium sheet joins in flask, use the tetrahydrofuran (THF) submergence, add 1～2 allyl bromide 98, 1 iodine, after initiation reaction, to be dissolved in mixed solution that the 5g tetrahydrofuran (THF) obtains by the 0.3g allyl bromide 98, to control drop rate be that 0.4～0.8ml/min is added drop-wise to wherein, after dropwising, make temperature of reaction maintain 10～20 ℃, again will be by the 0.01mol(1.7g of step (2) gained) 2, 6-dimethyl-6-methoxyl group enanthaldehyde be dissolved in the 10g tetrahydrofuran (THF), obtain 2, 6-dimethyl-6-methoxyl group enanthaldehyde solution, with the mixed solution that is formed by 1.4g allyl bromide 98 and 20g tetrahydrofuran (THF), all take drop rate as 0.4～0.8ml/min, add wherein, after dripping, at this temperature, continue stirring reaction 1h, the GC trace analysis, to 2, when 6-dimethyl-6-methoxyl group enanthaldehyde GC content was almost constant, reaction finished, slowly add 10% ammonium chloride solution 10mL cancellation reaction, layering, water layer methyl tertiary butyl ether extracting twice, merge organic layer, wash with water once, separate organic layer, to obtain organic layer under normal pressure 80-120 ℃ distill, except desolventizing, residuum carries out column chromatographic isolation and purification with the pillar of 30cm*3.5cmi.d, obtain the 1-allyl group-2 of GC content 96.5%, 6-dimethyl-6-methoxyl group enanthol,
Magnesium wherein, bromoalkane, the mol ratio of 2,6-dimethyl-6-methoxyl group enanthaldehyde is 1.3～1.6:1.2～1.5:1;
Above-mentioned gained final product passes through IR, HNMR, and the CNMR analyzing and testing, its analytical results is as follows:
IR：635w，743w，889w，918s，1094s，1250s，1395s，1454s，1649s，2906w，2993s，3461s，3676s。
1H-NMR(CDCl3)：0.85-0.95(m，3H)；1.14(s，6H)；1.21-2.39(m，10H)；3.15(s，3H)；3.40-3.60(m，1H)；5.10(m，2H)；5.85(m，1H).
13C-NMR(CDCl3)：135.59；117.58；74.57/74.49；73.04；49.01；40.14/39.12；38.29/37.85；33.70/32.64；24.95/24.97；24.91；24.91；21.55/21.39；13.83/15.22。
By above-mentioned analytical results, can be drawn, the final product of above-mentioned gained is 1-allyl group-2,6-dimethyl-6-methoxyl group enanthol.
The 1-allyl group-2 of above-mentioned gained, 6-dimethyl-6-methoxyl group enanthol is commented perfume (or spice) through the perfumer, determines that it has pleasant melon perfume and simple and elegant fragrance of a flower fragrance.
Foregoing is the basic explanation under conceiving for the present invention only, and, according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (5)
1. one kind 2,6-dimethyl-6-methoxyl group enanthol series derivates, is characterized in that describedly 2, and 6-dimethyl-6-methoxyl group enanthol series derivates has following structural formula:
Wherein R is ethyl, propyl group, sec.-propyl, butyl, isobutyl-, isopentyl, cyclopentyl, hexyl, cyclohexyl or allyl group.
2. as claimed in claim 1 a kind of 2, the synthetic method of 6-dimethyl-6-methoxyl group enanthol series derivates,
It is characterized in that specifically comprising the steps:
(1), alkylated reaction
Sulcatone and methyl alcohol are thrown in reaction flask, slowly added the vitriol oil, Sulcatone and methyl alcohol reaction generate 6-methyl-6-methoxyl group-2-heptanone under the catalysis of the vitriol oil;
Above-mentioned reaction process is controlled temperature 50-60 ℃, and the time is 18-28h;
Above-mentioned Sulcatone used, the amount of methyl alcohol and the vitriol oil is calculated in mass ratio, i.e. Sulcatone: methyl alcohol: and the vitriol oil is 100:250:13;
(2), Darzens condensation reaction
The 6-methyl of step (1) gained-6-methoxyl group-2-heptanone and ethyl chloroacetate are thrown in reaction flask, slowly added sodium alkoxide, under the effect of sodium alkoxide, 6-methyl-6-methoxyl group-2-heptanone and ethyl chloroacetate generation condensation reaction generate the epoxy carboxylicesters;
It is-10～-15 ℃ that above-mentioned condensation reaction is controlled temperature, and the time is 3～6h;
Above-mentioned condensation reaction 6-methyl used-6-methoxyl group-2-heptanone, ethyl chloroacetate and sodium alkoxide calculate in molar ratio, i.e. 6-methyl-6-methoxyl group-2-heptanone: ethyl chloroacetate: sodium alkoxide is 1:1.25:1.4;
After above-mentioned condensation reaction finishes, be down under room temperature the methanol solution that adds 2.25 molar equivalent sodium hydroxide and carry out saponification reaction, the saponification reaction process control temp is 50 ℃, time is 2～4h, after saponification fully, and 20KPa reclaim under reduced pressure methyl alcohol, treat no longer to go out cut, be incorporated as the frozen water of raw material 6-methyl-3～5 times of amounts of 6-methoxyl group-2-heptanone, stir the 10min left and right, stratification;
Remove the upper strata organic layer, lower floor's water methyl tertiary butyl ether extracting twice, remove the organic layer that extracts gained for twice, merges the water layer of twice extraction gained;
By the water layer after above-mentioned merging with mass percent concentration 35% concentrated hydrochloric acid regulate pH be after 5～6 again with methyl tertiary butyl ether extraction three times, merges the organic layer that extracts gained for three times;
By the organic layer after above-mentioned merging at 75～85 ℃ of distillating recovering solvents of normal pressure, in the gained enriched material, be incorporated as again the copper powder of its weight 1%, be heated to 150～180 ℃ carry out decomposition reaction 2～5h after, the 10KPa underpressure distillation, collect 62～66 ℃ of cuts and namely obtain 2,6-dimethyl-6-methoxyl group enanthaldehyde;
(3), 2, the addition reaction of 6-dimethyl-6-methoxyl group enanthaldehyde and Grignard reagent
the magnesium sheet of oven dry is joined in flask, use the tetrahydrofuran (THF) submergence, add 1～2 bromoalkane, 1 iodine, after adding thermal booster reaction, control drop rate and be 0.4～0.8ml/min and drip the mixed solution that the tetrahydrofuran (THF) by bromoalkane and 5～8 times of its weight forms, dropwise and react again the 1h left and right, in bathing, cryosel is cooled to-5～0 ℃, and then the control drop rate is that 0.4～0.8ml/min drips by 2 of step (2) gained, the mixed solution that 6-dimethyl-6-methoxyl group enanthaldehyde and tetrahydrofuran (THF) form, after dropwising, move to room temperature, the GC trace analysis, to raw materials used 2, when 6-dimethyl-6-methoxyl group enanthaldehyde GC detection level was almost constant, reaction finished, slowly add the ammonium chloride solution cancellation, layering, water layer methyl tertiary butyl ether extracting twice, merge organic layer, organic layer is washed once with deionized water, then separate organic layer, by the organic layer 80-120 ℃ under normal pressure that obtains, steam solvent, the residuum of gained carries out the column chromatography purification, obtain 2, 6-dimethyl-6-methoxyl group enanthol series derivates,
Magnesium wherein, bromoalkane, the mol ratio of 2,6-dimethyl-6-methoxyl group enanthaldehyde is 1.3～1.6:1.2～1.5:1;
Described bromoalkane is monobromethane, N-PROPYLE BROMIDE, bromine isopropyl alkane, n-butyl bromide, bromine Trimethylmethane, bromine iso-pentane, bromohexane, bromocyclopentane, bromocyclohexane or allyl bromide 98.
3. as claimed in claim 2 a kind of 2, the synthetic method of 6-dimethyl-6-methoxyl group enanthol series derivates,
It is characterized in that 2 described in step (3), in the mixed solution that 6-dimethyl-6-methoxyl group enanthaldehyde and tetrahydrofuran (THF) form, the amount of 2,6-dimethyl-6-methoxyl group enanthaldehyde and tetrahydrofuran (THF), press 2,6-dimethyl-6-methoxyl group enanthaldehyde: tetrahydrofuran (THF) is the ratio of 1mol:1000g.
4. as claimed in claim 3 a kind of 2, the synthetic method of 6-dimethyl-6-methoxyl group enanthol series derivates,
It is characterized in that the pillar used of the column chromatography described in step (3) is the pillar of 30cm*3.5cmi.d.
5. a kind of 2 as claimed in claim 1,6-dimethyl-6-methoxyl group enanthol series derivates can be used as spices and uses.
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| US10077414B2 (en) | 2016-07-29 | 2018-09-18 | Bedoukian Research, Inc. | Fragrance compositions containing isomeric alkoxynonenols |
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| US4287133A (en) * | 1978-11-17 | 1981-09-01 | International Flavors & Fragrances Inc. | 6-Hydroxy-2,6-dimethylheptanal, organoleptic uses thereof and processes for preparing the same |
| CN101906024A (en) * | 2010-07-29 | 2010-12-08 | 上海应用技术学院 | Method for preparing sandaler |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4287133A (en) * | 1978-11-17 | 1981-09-01 | International Flavors & Fragrances Inc. | 6-Hydroxy-2,6-dimethylheptanal, organoleptic uses thereof and processes for preparing the same |
| CN101906024A (en) * | 2010-07-29 | 2010-12-08 | 上海应用技术学院 | Method for preparing sandaler |
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| WO2015123984A1 (en) * | 2014-02-24 | 2015-08-27 | 南京运华立太能源科技有限公司 | Method for preparing 2,6-dimethyl-6-alkyloxy(or hydroxyl)heptaldehyde |
| US10077414B2 (en) | 2016-07-29 | 2018-09-18 | Bedoukian Research, Inc. | Fragrance compositions containing isomeric alkoxynonenols |
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