CN1308054A - (3S,4S) and (3R,4R)-beta-methyl-gamma-hydroxy-alkyl nitrile and its preparation and use - Google Patents
(3S,4S) and (3R,4R)-beta-methyl-gamma-hydroxy-alkyl nitrile and its preparation and use Download PDFInfo
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Abstract
The present invention relates to a (3S, 4S) and (3R, 4R)-beta-methyl-gamma-hydroxy-alkyl nitrile, its preparation method and application. Said compound is made up by implement asymmetric Evansaldol condensation of chiral propionyl compound and aldehyde reaction, sulfonylation and cyanidation, and said compound can be used for preparing 3-methyl-4-alkyl-gamma-butyrolactone with optical activity.
Description
The present invention relates to a kind of (3S, 4S) and (3R, 4R)-b-methyl-gamma-hydroxy-alkyl nitrile, Preparation method and use.This compounds carries out asymmetric Evansaldol condensation by chirality propionyl compound and aldehyde, again through reduction, sulfonylation, cyaniding and getting.This compound can be used for preparing the optically active 3-methyl of tool-4-alkyl-gamma-butyrolactone 3 and 4.
Compound
Activeconstituents (Tsuneda, Fumihiko Jpn.Kokai Tokkyo Koho JP 09169624 A2 30 Jun 1997 Heisei, 7 (Japan) .APPLICATION:JP95-349861,21 Dec 1995 for the sterilizing oral agent; Chem.Abstr.1997,127:99565).An exemplary special case thing wherein, R
1=n-hexyl, the important chemical composition of the delicate fragrance that gives out at night for the orchid Aerngis confusa that originates in African Kenya and Tanzania and Aerangis Kirkii.This compound also is one of the volatile constituent of sweet orange (Citrus sinensis L.Osbeck) juice (N f, R.; Velluz, A.; Meyer, A.P.J.Essent.Oil Res., 1996,8,587-595.).Another exemplary special case thing, R
1=normal-butyl is commonly referred to Whiskey lactone, is Whiskey wine and flavoring ingredient vinous (Ebata, T.; Matsumoto, K.; Koseki, K.; Kawakami, H.; Matsushita, H.; Yoshikoshi, H.; Okaniwa, M.PCT Int.Appl.WO9212143 A1 23 Jul 1992,17pp.APPLICATION:WO91-JP1780 27 Dec 1991; Chem.Abstr.118:22136.), the seasonings of tobacco (Suhara, S.; Matsuzaki, T.; Yoshikoshi, H.; Okaniwa.M.Jpn.Kokai Tokkyo Koho JP04207185 A2 29 Jul 1992 Heisei, (Japan) .APPLICATION:JP90-338646 30 Nov 1990; Chem.Abstr.117:230355.), the active ingredient of wormer (Shiono, Y.; Tsukasa, H.Jpn.Kokai Tokkyo Koho, JP63048203 A2 29Feb 1988 Showa, APPLICATION:JP86-193488 19 Aug 1986; And necessary component or additive (Yamaguchi, the M. of food, medicine, sterilant etc. Chem.Abstr.110:168109); Inanaga, J.Jpn.Kokai Tokkyo Koho JP63068578 A2 28 Mar 1988Showa, APPLICATION:JP86-214507 11 Sep 1986; Chem.Abstr 110:154131), reach perfume (Zaslona, A.Patentschrift (Switz.) CH685390 A 30 Jun 1995, APPLICATION:CH93-475 16 Feb 1993; Chem.Abstr 124:29588).Non-optical active compound 3 is or/and have a lot of record ((a) Shono, T. in 4 the synthetic document; Matsumura, Y.; Kashimura, S.; Hatanaka, K., J.Am.Chem.Soc., 1979,101,4752-3. (b) Pratt, A.J.; Thomas, E.J., Chem.Soc., Perkin Trans.1,1989,1521-27. (c) Costisella, B.; Gross, H.; Schick, H.Tetrahedron, 1984,40 (4), 733-6 (d) Takabe, K.; Yoda, H.; Iwabuchi, M.; Tanaka, M.Jpn.Kokai Tokkyo Koho JP02218673 A2 31 Aug 1990 HeiSei, APPLICATION:JP89-39466 21 Feb 1989; Chem.Abstr.114:61913 (e) Yoda, H.; Iwabuchi, M.; Fukuyo, A.; Tanaka, M.; Takabe, K.Chem.Express, 1989,4 (3), 165-8. (f) Yamaguchi, M.; Inanaga, J.Jpn.Kokai Tokkyo Koho, JP63068578 A2 28 Mar 1988 Showa, APPLICATION:JP86-214507 11 Sep 1986; Chem.Abstr 110:154131. (g) Ebata, T.; Kawakami, H.; Matsushita, H.Jpn.Kokai Tokkyo Koho, JP05086045 A2 6 Apr 1993 Heisei, APPLICATION:JP91-270510 24 Sep 1991; Chem.Abstr.119:225799. (h) Tsuno, T.; Sugiyama, K.Chem.Express, 1992,7 (12), 901-4. (i) Ebata, T.; Matsumoto, K.; Koseki, K.; Kawakami, H.; Matsushita, H.; Yoshikoshi, H.; Okaniwa, M.PCT Int.Appl.WO9212143 A123 Jul 1992, APPLICATION:WO91-JP1780 27 Dec 1991; Chem.Abstr.118:22136. (j) Tsukasa, H.Yukagaku, 1992,41 (5), 410-16 (Japanese) 1992; Chem.Abstr.117:90066. (k) Ma, S.; Shi, Z.; Yu, Z.Tetrahedron, 1999,55 (41), 12137-12148.).Synthetic then less ((a) Larcheveque, the M. of optical activity enantiomorph; Tamagnan, G.; Petit, Y.J.Chem.Soc., Chem.Commun., 1989,31-3. (b) Ebata, T.; Matsumoto, K.; Yoshikoshi, H.; Koseki, K.; Kawakami, H.; Okano, K.; Matsushita, H.Heterocycles, 1993,36 (5), 1017-26. (c) Marino, J.P.; Fernandez de la Pradilla, R.Tetrahedron Lett., 1985,26,5381-4.).Document (a) carries out conjugate addition with the methyl copper lithium reagent after with the hydroxy aldehyde of chirality and Meldrum's acid condensation and sets up second chiral centre, document (b) then with optically active trans-the Whiskey lactone is that raw material carries out configuration reversal and gets cis Whiskey lactone.Document (c) adopts chiral sulfoxide to induce new chiral centre.Recently, Kitahara etc. have reported the lactone 3 of R=n-hexyl and synthetic (Masuzawa, the Y. of 4 optical activity enantiomorph; Tamogami, S.; Kitahara, T.Nat.Prod.Lett.1999,13,239-246; Kitahara, T.; Masuzawa, Y.Jpn.Kokai Tokkyo Kobo, JP200086647 A2 28 Mar 2000, Chem.Abstr.2000,132:222392).They adopt asymmetric lactone
Be raw material, lactone be reduced into hemiacetal, and then form acetal with hexanol with DIBAL (diisobutyl aluminum alkane).With two key oxidation scissions, modify respectively again.Need the reaction of 8 steps altogether, wherein some step yield is very low.Reagent that relates to such as DIBAL, LiBHEt
3(lithium triethylborohydride) waits to be water vapor, and oxygen is extremely responsive, dangerous, and the expensive pharmaceutical chemicals of domestic no manufacturer production.Used asymmetric lactone ((1S, 5R)-2-oxabicyclo[3.3.0]-oct-6-en-3-one or (1R, 5S)-2-oxabicyclo[3.3.0]-oct-6-en-3-one) also expensive (for example, Aldrich2000/2001 price: (1R, 5S) $50/lg; (1S, 5R) $40/500mg) is not thing cheap and easy to get.
The purpose of this invention is to provide a kind of Beta-methyl-γ-hydroxyl one alkyl nitrile compound.
Another object of the present invention provides a kind of method for preparing above-claimed cpd.
The present invention also provides a kind of purposes of above-claimed cpd.
A kind of Beta-methyl-γ provided by the invention-hydroxyl-alkyl nitrile compound, its molecular formula is:
R wherein
1=C
3-C
10Alkyl.
The method for preparing above-claimed cpd of the present invention can be represented by following reaction expression:
R in the reaction formula
1Be C
3-C
10Alkyl, R
2And R
3Be hydrogen, phenyl, sec.-propyl or benzyl, R
2During for hydrogen, R
3Be phenyl, sec.-propyl, benzyl, R
3During for hydrogen, R
2Be phenyl, sec.-propyl, benzyl; R
4Be pTs (p-toluenesulfonyl) or Ms (methylsulfonyl), X=O (oxygen), S, (sulphur).The present invention adopts the asymmetric Aldol condensation of Evans ((a) Evans, D.A.; Bartroli, J.; Shih, T.L.J.Am.Chem.Soc.1981,103,2127-2129. (b) Evans, D.A.; Rieger, D.L.; Bilodeau, M.T.; Urpi, F.J.Am.Chem.Soc.1990,113,1047-1049.) set up two chiral centres in the product.(be S, S or R R) can (oxazoline prothetic group (when being X=O) be referring to Wu Yikang, Shen Xin, CN00116879.7 in it by used chirality prothetic group 6 for the configuration of two chiral centres that generated; Sulphur azoles quinoline thioketones prothetic group (when being X=S) is referring to Delaunay, D.; Toupet, L.; Corre, M.L.J.Org.Chem.1995,60, configuration 6604-6607.) and reaction conditions can very effective controls.In the presence of organic amine, in organic solvent, react.Temperature of reaction is-80～+ 40 ℃, and the reaction times is 0.1～40h, and used reactant molar ratio is a compound 7: compound 8: titanium tetrachloride or di-n-butyl boron triflate: organic amine=1: 0.5～10: 0.5～10: 0.5～10.Described organic amine is a triethylamine, diisopropyl ethyl amine, N, N-Tetramethyl Ethylene Diamine, N, N-4-methyl-diaminopropane, sparteine (Sparteine) etc.Reaction times is 0.1～40h.
The chirality prothetic group is removed in above-mentioned condensation product 9 usefulness metal borohydrides or the hydrogen reduction of aluminium lithium, accordingly 1,3-glycol 10.Described metal borohydride is lithium boron hydrogen, sodium borohydride, potassium boron hydrogen, calcium boron hydrogen, zinc boron hydrogen.Temperature of reaction is-80～+ 40 ℃.The mol ratio of reactant and reductive agent is 1: 0.25～20.Reaction times is 0.1～40h.
Above-mentioned gained glycol 10 is through optionally being converted into primary hydroxyl methanesulfonates or p-toluenesulfonic esters 11 with methylsulfonyl chloride or Tosyl chloride in the presence of organic amine.Glycol 10: the mol ratio of methylsulfonyl chloride or Tosyl chloride is 1: 1～5.Temperature of reaction is-80～+ 80 ℃, and the reaction times is 0.1～40h.Described organic amine is a triethylamine, arsenic pyridine, diisopropyl ethyl amine, N, N-Tetramethyl Ethylene Diamine, N, N-4-methyl-diaminopropane, sparteine (Sparteine) etc.
Above-mentioned product methanesulfonates or p-toluenesulfonic esters 11 provide corresponding nitrile compound 1 or 2 with sodium cyanide or potassium cyanide reaction.Temperature of reaction is-10～+ 180 ℃.Reaction times is 0.2～80h.Methanesulfonates or p-toluenesulfonic esters 11 are 1: 1～20 with the mol ratio of sodium cyanide or potassium cyanide.
Above-mentioned reaction is all carried out in organic solvent, and described organic solvent can be a methylene dichloride, chloroform, tetrahydrofuran (THF), methyl alcohol, ethanol, Virahol, the trimethyl carbinol, chloroform, methyl-sulphoxide (DMSO), N, N '-dimethyl formamide or 1,4-dioxane etc.Evans condensation reaction and sulfonylation are recommended to use solvent to be methylene dichloride, chloroform, tetrahydrofuran (THF) etc.; reduction reaction recommends to use solvent to be tetrahydrofuran (THF), methyl alcohol, ethanol; Virahol; the trimethyl carbinols etc., cyanogenation are recommended to use solvent to be methyl-sulphoxide (DMSO), N; N '-dimethyl formamide; 1, the 4-dioxane, or tetrahydrofuran (THF) etc.
Nitrile compound of the present invention can be used to prepare the optically active 3-methyl of tool-4-alkyl-gamma-butyrolactone 3 or 4.(or earlier in pH＞8～14 time hydrolysis again in pH＜0.01～5 time cyclization) reacts to such an extent that 5-person encircles target lactone compound 3 or 4 above-claimed cpd 1 or 2 in pH＜0.01～5.Reaction solvent is water or organic solvent or the two mixture.Organic solvent can be methyl alcohol, ethanol, tetrahydrofuran (THF), methyl-sulphoxide, N, N '-dimethyl formamide, 1,4-dioxane etc.Reaction times is 0.2～80h, and temperature of reaction is-10～+ 180 ℃.Be that compound 1 or 2 can be used to prepare sterilant, spices, seasonings, wormer, the additive of food or medicine etc.And the preparation method of compound 1 or 2 is also very easy.
The present invention will be helped to understand by following examples, but content of the present invention can not be limited.
Embodiment 1
N-propionyl-(S)-4-benzyl-sulphur azoles quinoline-2-thioketones (1mmol) is dissolved in methylene dichloride (5ml), and the ice-water bath cooling drips TiCl down
4(1～5mmol).Stir and add sparteine (2mmol) after 10～50 minutes.Add enanthaldehyde (1～2mmol) then.Behind reaction 1～2h, add the shrend reaction of going out, ether dilutes, and tells organic phase, dried over sodium sulfate, and silica gel column chromatography must slightly yellowy oily product, yield 60%.
1HNMRδ7.40-7.22(m,5H),5.36(m,1H),4.50(dq,J=3.0,6.9Hz,1H),3.94(m,1H),3.41(dd,J=6.4,11.3Hz,1H),3.23(dd,J=3.8,13.2Hz,1H),2.29(d,J=11.5Hz,1H),2.64(OH,1H),1.40-1.20(m,10H),1.26(d,J=8.6Hz,3H),0.89(t,J=6.7HZ,3H).IR(film):3400,1695,1604,1585,1496,1455,1342,1262,1164,1030,744,702cm
-1.
Embodiment 2
N-propionyl-(R)-4-phenyl-oxazolines-2-ketone (1mmol) is dissolved in methylene dichloride (5ml), and-78 ℃ of coolings add triethylamine (1.2mmol) and Bu down
2BOTf (1mmol).After stirring 1h.Add n-hexyl aldehyde (2mmol) then.Behind the reaction 1h, add the shrend reaction of going out, drip 30% hydrogen peroxide (1ml) again.Reaction solution dilutes with ether, tells organic phase, dried over sodium sulfate, and silica gel column chromatography must slightly yellowy oily product, yield 80%.
1HNMRδ7.3-7.1(m,5H),5.6(t,J=8Hz,1H),4.9(m,1H),4.7(m,2H),4.1(m,1H),1.6-1.3(m,8H),1.3(d,J=7Hz,3H),0.91(t,J=7Hz,3H).IR(film):3520,1778,1690,1605,1455,1390,1210cm
-1.
Embodiment 3
N-(2-methyl-3-hydroxyl)-hexanoyl-(S)-4-benzyl-sulphur azoles quinoline-2-thioketones (1mmol) is dissolved in ethanol (5ml).Stir and add NaBH down
4(100mg).Pressure reducing and steaming solvent after raw material disappears, residue ether extraction, washing, Na
2SO
4Drying, silica gel column chromatography get the colorless oil product, yield 90%.
1HNMRδ3.8(brs,1H),3.70(m,2H),2.20(brs,1H),2.09(brs,1H),1.80(m,1H),1.57-1.20(m,4H),0.98(t,J=6.5Hz,3H),0.90(t,J=6Hz,3H).IR(film)3350,1460,1033cm
-1.MSm/z:132(M+,0.9),114(8),97(45),55(100),43(87).
Embodiment 4
(2S, 3S)-the 2-methyl isophthalic acid, 3-dodecanediol (1mmol) and triethylamine (5mmol) are dissolved in methylene dichloride (5ml), and the ice bath cooling adds Tosyl chloride (1.5mmol) down.React 1～20h under the room temperature.With ether dilution, washing, Na
2SO
4Drying, silica gel column chromatography gets colorless oil, yield 95%.
1HNMRδ7.80(d,J=8.2Hz,2H),7.36(d,J=8.2Hz,2H),4.08(dd,J=8.0,9.6Hz,1H),3.91(dd,J=6.1,9.6Hz,1H),3.69(m,1H),2.45(s,3H),1.90(m,1H),1.60-1.20(m,16H),0.90(t,J=6.0Hz,3H),0.89(d,J=7.4Hz,3H).IR(film)3552,1598,1465,1357,1180,965,815,666cm
-1.
Embodiment 5
(2R, 3R)-2-propyl group-1,3-heptanediol-1-methanesulfonates (1mmol) is dissolved in methyl-sulphoxide (5ml), and (1～10mmol), thin up behind the stirring reaction 20h is used ether extraction, washing, Na to add sodium cyanide
2SO
4Drying, silica gel column chromatography get the colorless oil product, yield 92%.
1HNMRδ3.73(m,1H),3.62(brs,1H),2.50(dd,J=7.0,17Hz,1H),2.30(dd,J=7.7,17Hz,1H),1.98(m,1H),1.51(m,1H),1.62(OH),1.79-1.20(m,6H),1.01(d,J=7Hz,3H),0.90(t,J=7Hz,3H).IR(film)3459,2248cm
-1.
Embodiment 6
(3S, 4S)-3-methyl-4-hydroxyl-certain herbaceous plants with big flowers nitrile (1mmol) is dissolved in ethanol (5ml), adds the 2MNaOH aqueous solution (1ml), is chilled to room temperature behind the back flow reaction 8h, and the pressure reducing and steaming solvent adds tetrahydrofuran (THF) (5ml) and 1MH
2SO
4(1ml) room temperature reaction 8h, the dilution that adds diethyl ether, washing, Na
2SO
4Drying, silica gel column chromatography get the pleasant aromatic odour colorless oil of tool product, yield 95%.
1HNMRδ4.42(m,1H),2.63(dd,J=7.8,16.8Hz,1H),2.56(m,1H),2.16(dd,J=3.7,16.8Hz,1H),1.70-1.20(m,10H),0.98(d,J=7.1Hz,3H),0.86(t,J=6.8Hz,3H).IR(film)1779cm
-1.MSm/z142(M
+-42,14),105(10),92(28),91(40),86(23),83(15),69(28),57(100).
Claims (7)
1. one kind (3S, 4S) and (3R, 4R)-Beta-methyl-γ-hydroxyl-alkyl nitrile, its molecular formula is shown in 1 and 2:
, R wherein
1=C
3-C
10Alkyl.
2. the preparation method of a nitrile compound as claimed in claim 1 is characterized in that making through following method:
(1) in organic solvent, under titanium tetrachloride or di-n-butyl boron triflate and the organic amine effect, compound 7 and 8 carries out asymmetric Evans aldol condensation and gets compound 9, temperature of reaction is-80～+ 40 ℃, reaction times is 0.1～40h, the mol ratio of above-claimed cpd is a compound 7: compound 8: titanium tetrachloride or di-n-butyl boron triflate: organic amine=1: 0.5～10: 0.5～10: 0.5～10, described organic amine is a triethylamine, diisopropyl ethyl amine, N, N-Tetramethyl Ethylene Diamine, N, the N-4-methyl-diaminopropane, sparteine;
(2) in organic solvent, the chirality prothetic group is removed in compound 9 usefulness metal borohydrides or the hydrogen reduction of aluminium lithium, get corresponding compounds 10, temperature of reaction is-80～+ 40 ℃, reaction times is 0.1～40h, the mol ratio of reactant and reductive agent is 1: 0.25～20, and described metal borohydride is lithium boron hydrogen, sodium borohydride, potassium boron hydrogen, calcium boron hydrogen, zinc boron hydrogen;
(3) in organic solvent, compound 10 usefulness methylsulfonyl chlorides or Tosyl chloride are converted into methanesulfonates or p-toluenesulfonic esters with primary hydroxyl in the presence of organic amine, temperature of reaction is-80～+ 80 ℃, and the reaction times is 0.1～40h, the mol ratio of compound 10, methylsulfonyl chloride or Tosyl chloride is 1: 1～5, described organic amine is a triethylamine, diisopropyl ethyl amine, N, the N-Tetramethyl Ethylene Diamine, N, N-4-methyl-diaminopropane, sparteine;
(4) in organic solvent, the mol ratio of the product of above-mentioned (3) and sodium cyanide or potassium cyanide is 1: 0.5～20 o'clock, at-10～+ 180 ℃ of reaction 0.2～80h, provides corresponding compounds 1 or 2;
Above-claimed cpd 7,8,9 and the following molecular formula of 10 tools:
R wherein
2R during for hydrogen
3Be phenyl, sec.-propyl, benzyl, R
3R during for hydrogen
2Be phenyl, sec.-propyl, benzyl; X=O or S, R
1Be C
3-C
10Alkyl.
3. preparation method as claimed in claim 2 is characterized in that directly carrying out selectivity tosylation or methylsulfonylization with the compound 10 of metal borohydride or aluminium lithium hydrogen reduction compound 9 gained without protection.
4. preparation method as claimed in claim 2 is characterized in that the single p-toluenesulfonic esters or the not purified cyanogenation that directly carries out of methanesulfonates of the compound 10 of gained.
5. preparation method as claimed in claim 2 is characterized in that described organic solvent can be a methylene dichloride, chloroform, tetrahydrofuran (THF), methyl alcohol, ethanol, Virahol, the trimethyl carbinol, chloroform, methyl-sulphoxide (DMSO), N, N '-dimethyl formamide or 1,4-dioxane.
6. the purposes of nitrile compound according to claim 1 is characterized in that being used to prepare sterilant, spices, seasonings, wormer, the additive of food or medicine.
7. the purposes of nitrile compound according to claim 1, it is characterized in that being used for preparation (3S, 4S) and (3R, 4R)-cis-3-methyl-4-alkyl-gamma-butyrolactone.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936703A (en) * | 2013-01-17 | 2014-07-23 | 上海朴颐化学科技有限公司 | Preparation method of 5-oxaspiro[2,4]heptane-6-one and intermediate thereof |
| CN116693432A (en) * | 2023-08-09 | 2023-09-05 | 山东国邦药业有限公司 | Preparation method of florfenicol intermediate D-ethyl ester |
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2001
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936703A (en) * | 2013-01-17 | 2014-07-23 | 上海朴颐化学科技有限公司 | Preparation method of 5-oxaspiro[2,4]heptane-6-one and intermediate thereof |
| CN116693432A (en) * | 2023-08-09 | 2023-09-05 | 山东国邦药业有限公司 | Preparation method of florfenicol intermediate D-ethyl ester |
| CN116693432B (en) * | 2023-08-09 | 2023-10-20 | 山东国邦药业有限公司 | Preparation method of florfenicol intermediate D-ethyl ester |
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