JPH10175902A - Ring opening of epoxy compound - Google Patents
Ring opening of epoxy compoundInfo
- Publication number
- JPH10175902A JPH10175902A JP8359666A JP35966696A JPH10175902A JP H10175902 A JPH10175902 A JP H10175902A JP 8359666 A JP8359666 A JP 8359666A JP 35966696 A JP35966696 A JP 35966696A JP H10175902 A JPH10175902 A JP H10175902A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- epoxy compound
- alcohol
- butylene oxide
- mol
- 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.)
- Pending
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 19
- 239000004593 Epoxy Substances 0.000 title claims abstract description 18
- 238000007142 ring opening reaction Methods 0.000 title claims 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 8
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 13
- CSZZMFWKAQEMPB-UHFFFAOYSA-N 1-methoxybutan-2-ol Chemical compound CCC(O)COC CSZZMFWKAQEMPB-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 abstract description 15
- 230000015572 biosynthetic process Effects 0.000 abstract description 14
- 239000003112 inhibitor Substances 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 238000002329 infrared spectrum Methods 0.000 description 13
- 239000007795 chemical reaction product Substances 0.000 description 12
- 238000004817 gas chromatography Methods 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 230000008034 disappearance Effects 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 238000004821 distillation Methods 0.000 description 7
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 238000005292 vacuum distillation Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000013076 target substance Substances 0.000 description 3
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2-methyl-5-methylpyridine Natural products CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 2
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- SLRCCWJSBJZJBV-AJNGGQMLSA-N sparteine Chemical compound C1N2CCCC[C@H]2[C@@H]2CN3CCCC[C@H]3[C@H]1C2 SLRCCWJSBJZJBV-AJNGGQMLSA-N 0.000 description 2
- 229960001945 sparteine Drugs 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WSSVWDSNMLWCDJ-SECBINFHSA-N (2r)-1-methoxyoctan-2-ol Chemical compound CCCCCC[C@@H](O)COC WSSVWDSNMLWCDJ-SECBINFHSA-N 0.000 description 1
- NJWSNNWLBMSXQR-MRVPVSSYSA-N (2r)-2-hexyloxirane Chemical compound CCCCCC[C@@H]1CO1 NJWSNNWLBMSXQR-MRVPVSSYSA-N 0.000 description 1
- DEUJSGDXBNTQMY-UHFFFAOYSA-N 1,2,2-trifluoroethanol Chemical compound OC(F)C(F)F DEUJSGDXBNTQMY-UHFFFAOYSA-N 0.000 description 1
- ZBNXMTHJYVSJGZ-UHFFFAOYSA-N 1-phenylmethoxybutan-2-ol Chemical compound CCC(O)COCC1=CC=CC=C1 ZBNXMTHJYVSJGZ-UHFFFAOYSA-N 0.000 description 1
- LHVVHKMPOOYTEZ-UHFFFAOYSA-N 1-propan-2-yloxybutan-2-ol Chemical compound CCC(O)COC(C)C LHVVHKMPOOYTEZ-UHFFFAOYSA-N 0.000 description 1
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- AKHOMSOLYZQWKM-UHFFFAOYSA-N 2-(methoxymethyl)-3-methyloxirane Chemical compound COCC1OC1C AKHOMSOLYZQWKM-UHFFFAOYSA-N 0.000 description 1
- NJWSNNWLBMSXQR-UHFFFAOYSA-N 2-hexyloxirane Chemical compound CCCCCCC1CO1 NJWSNNWLBMSXQR-UHFFFAOYSA-N 0.000 description 1
- 229930008564 C01BA04 - Sparteine Natural products 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- SLRCCWJSBJZJBV-UHFFFAOYSA-N alpha-isosparteine Natural products C1N2CCCCC2C2CN3CCCCC3C1C2 SLRCCWJSBJZJBV-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- JSTRAGDNVJZRJA-UHFFFAOYSA-N cyclopenta-1,3-diene 2-cyclopenta-2,4-dien-1-yl-N,N-dimethylethanamine iron(2+) Chemical compound [Fe++].c1cc[cH-]c1.CN(C)CC[c-]1cccc1 JSTRAGDNVJZRJA-UHFFFAOYSA-N 0.000 description 1
- UNMQCGHIBZALKM-YCBDHFTFSA-N cyclopenta-1,3-diene;(1r)-1-cyclopenta-2,4-dien-1-yl-n,n-dimethylethanamine;iron(2+) Chemical compound [Fe+2].C=1C=C[CH-]C=1.CN(C)[C@H](C)C1=CC=C[CH-]1 UNMQCGHIBZALKM-YCBDHFTFSA-N 0.000 description 1
- WAJNQUGXOWDSHH-UHFFFAOYSA-N cyclopenta-1,3-diene;2-cyclopenta-2,4-dien-1-ylethanamine;iron(2+) Chemical compound [Fe+2].C=1C=C[CH-]C=1.NCC[C-]1C=CC=C1 WAJNQUGXOWDSHH-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【産業上の利用分野】この発明は、エポキシ環を開環
し、アルコキシ化化合物を製造する方法に関するもので
あって、当該化合物を工業的に製造する方法を提供する
ものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an alkoxylated compound by opening an epoxy ring, and to a method for producing the compound industrially.
【０００２】[0002]
【従来の技術】エポキシ化合物を開環する方法として知
られているものに、１−メトキシ−２，３−エポキシブ
タンを、ソジウムとメタノールにから調製された溶液の
中で、還流し、１，２−ジメトキシ−３−ブタノールを
得る方法がある（ｖｏｌ．７６７０９．１９５４）。
１，２−エポキシブタンをソジウムメトキシドと共に加
熱する方法や酸性メタノールと加熱する方法が知られて
いる（Ｊ．Ｃ．Ｓ．１９５９ ５６７）。2. Description of the Related Art In a known method for opening a ring of an epoxy compound, 1-methoxy-2,3-epoxybutane is refluxed in a solution prepared from sodium and methanol. There is a method for obtaining 2-dimethoxy-3-butanol (vol. 76709.1954).
A method of heating 1,2-epoxybutane with sodium methoxide and a method of heating with acidic methanol are known (JCS 1959 567).
【０００３】[0003]
【発明が解決しようとする課題】本発明は、エポキシ化
合物とアルコール類とを反応させエポキシ環を開環し、
隣る炭素原子に水酸基を結合したアルコキシ化化合物を
製造するに際して、高い純度で目的物を得ることができ
且つ工業的製造にも適している方法を提供せんとするも
のである。DISCLOSURE OF THE INVENTION The present invention provides a method for reacting an epoxy compound with an alcohol to open an epoxy ring,
It is an object of the present invention to provide a method capable of obtaining a target product with high purity and suitable for industrial production when producing an alkoxylated compound in which a hydroxyl group is bonded to an adjacent carbon atom.
【０００４】[0004]
【課題を解決するための手段】エポキシ化合物とアルコ
ールとを反応させてエポキシ環を開環し、隣る炭素原子
にアルコキシ基を有するアルコールを製造するに際し、
アミン取り分け第三級アミンを存在させることによって
発明の目的が達成される。即ち、従来使用されてきたア
ルコラートのごとき強いアルカリ性物ではなく、また水
と爆発的に反応する危険もない第三級アミンを触媒量の
使用で反応を完結せしめるというものである。In producing an alcohol having an alkoxy group at an adjacent carbon atom by reacting an epoxy compound with an alcohol to open an epoxy ring,
The purpose of the invention is achieved by the presence of the tertiary amine, especially the amine. That is, the reaction is completed by using a tertiary amine which is not a strong alkaline substance such as a conventionally used alcoholate and which does not have a risk of explosively reacting with water in a catalytic amount.
【０００５】本発明において使用されるエポキシ化合物
としては、１，２−ブチレンオキシド、エチレンオキシ
ド、プロピレンオキシド、シクロヘキセンオキシド、
１，２−エポキシオクタンなどが挙げられる。次に、使
用されるアルコール類としては、メタノール、エタノー
ル、プロパノール、イソプロパノール、イゾブタノー
ル、ｔ−ブタノール、ベンジルアルコール、アリルアル
コール、トリフルオロエタノールなどが挙げられる。The epoxy compound used in the present invention includes 1,2-butylene oxide, ethylene oxide, propylene oxide, cyclohexene oxide,
1,2-epoxyoctane and the like. Next, examples of the alcohol used include methanol, ethanol, propanol, isopropanol, isobutanol, t-butanol, benzyl alcohol, allyl alcohol, and trifluoroethanol.
【０００６】第三級アミンとしては、トリエチルアミ
ン、ジメチルアニリン、１，８−ジアザビシクロ［５．
４．０］ウンデセン−７、ピリジン、２，６−ルチジ
ン、スパルテイン、Ｎ，Ｎ−ジメチルフェロセンエチル
アミン、（−）−スパルテイン、Ｒ−（＋）−Ｎ，Ｎ−
ジメチル−１−フェロセニルエチルアミンなどが挙げら
れる。これら第三級アミンの使用量は触媒量でよいけれ
ども、少ないときは反応完了までに時間がかかることと
なる。例えば１，８−ジアザビシクロ［５．４．０］ウ
ンデセン−７を使用する場合、原料のオキシド化合物１
モルに対し、０．０４以上使用することが好都合であ
る。As the tertiary amine, triethylamine, dimethylaniline, 1,8-diazabicyclo [5.
4.0] Undecene-7, pyridine, 2,6-lutidine, sparteine, N, N-dimethylferroceneethylamine, (-)-sparteine, R-(+)-N, N-
Dimethyl-1-ferrocenylethylamine and the like. Although the amount of these tertiary amines used may be a catalytic amount, when the amount is small, it takes time to complete the reaction. For example, when 1,8-diazabicyclo [5.4.0] undecene-7 is used, the starting oxide compound 1
It is convenient to use 0.04 or more based on mole.
【０００７】本発明の反応は、エポキシ化合物、アルコ
ール類及び第三級アミンを混合し、撹拌しながら加温乃
至加熱することによって実施されるところ、反応中にエ
ポキシ化合物が二つ以上結合した多量体の生成が懸念さ
れるので、これを抑制するために、重合禁止剤を加える
ことが効を奏することがわかった。重合禁止剤として
は、ハイドロキノン、ハイドロキノンモノメチルエーテ
ルなどが挙げられる。The reaction of the present invention is carried out by mixing an epoxy compound, an alcohol and a tertiary amine and heating or heating the mixture with stirring. Since formation of a body is concerned, it has been found that adding a polymerization inhibitor is effective to suppress this. Examples of the polymerization inhibitor include hydroquinone and hydroquinone monomethyl ether.
【０００８】[0008]
【実施例】本発明をさらに具体的に説明するために実施
例を記述する。尚、実施例の記述において１，８−ジア
ザビシクロ［５．４．０］ウンデセン−７をＤＢＵと略
記する。 実施例１ １−メトキシ−２−ブタノールの合成：１００ｍｌ３径
フラスコに，メタノール５ｍｌ、ＤＢＵ２．１０ｇ（１
３．８ｍｍｏｌ）を仕込み、１，２−ブチレンオキシド
５．０ｇ（６９．３ｍｍｏｌ）を室温にて滴下した。そ
の後５０℃で６時間反応しガスクロマトグラフィーにて
原料消失の確認を行い反応の終点とした。反応終了後、
反応生成物は、そのまま減圧蒸留にて精製を行い目的物
たる無色液体を得た。 得量３．４２ｇ（収率４７．３
６％）１ Ｈ−ＮＭＲスペクトル（ＣＤＣｌ３，ｐｐｍ）：０．
９７（ｔ３Ｈ），１．４６〜１．５０（ｍ２Ｈ），２．
２６（ｄ１Ｈ），３．２４（ｔ１Ｈ），３．３９〜３．
４３（ｍ４Ｈ），３．６９〜３．７０（ｍ１Ｈ） ＩＲ スペクトル（ｎｅａｔ，ｃｍ−１）：３４３６，
２９６５，２９６７，２８８１，１４６１，１１１０，
９２０，５６１ 沸点 １３５℃／７６０ｍｍＨｇEXAMPLES Examples will be described in order to more specifically explain the present invention. In the description of Examples, 1,8-diazabicyclo [5.4.0] undecene-7 is abbreviated as DBU. Example 1 Synthesis of 1-methoxy-2-butanol: In a 100-ml 3-diameter flask, 5 ml of methanol and 2.10 g of DBU (1
(3.8 mmol), and 5.0 g (69.3 mmol) of 1,2-butylene oxide was added dropwise at room temperature. Thereafter, the reaction was carried out at 50 ° C. for 6 hours, and the disappearance of the raw materials was confirmed by gas chromatography, which was regarded as the end point of the reaction. After the reaction,
The reaction product was purified as it was by distillation under reduced pressure to obtain a colorless liquid as a target product. 3.42 g (yield 47.3 g)
6%) 1 H-NMR spectrum (CDCl 3 , ppm): 0.1.
97 (t3H), 1.46 to 1.50 (m2H),
26 (d1H), 3.24 (t1H), 3.39-3.
43 (m4H), 3.69 to 3.70 (m1H) IR spectrum (neat, cm -1 ): 3436,
2965, 2967, 2881, 1461, 1110,
920,561 Boiling point 135 ° C / 760mmHg
【０００８】実施例２ １−メトキシ−２−ブタノールの合成：１００ｍｌ３径
フラスコにメタノール６ｍｌ，ＤＢＵ０．８４ｇ（５．
５ｍｍｏｌ）を仕込み１，２−ブチレンオキシド１０．
０ｇ（１３７．８ｍｍｏｌ），を室温にて滴下した。そ
の後５０℃〜６０℃で８時間反応しガスクロマトグラフ
ィーにて原料消失の確認を行い反応の終点とした。反応
終了後、反応生成物は、そのまま減圧蒸留にて精製を行
い目的物たる無色液体を得た。 得量 ８．８７ｇ（収
率 ６１．４３％）１ Ｈ−ＮＭＲスペクトル、ＩＲスペクトル、沸点は実施
例１で得たものと同一であった。Example 2 Synthesis of 1-methoxy-2-butanol: 6 ml of methanol and 0.84 g of DBU (5.
5 mmol) and 1,2-butylene oxide.
0 g (137.8 mmol) was added dropwise at room temperature. Thereafter, the reaction was carried out at 50 ° C. to 60 ° C. for 8 hours, and the disappearance of the raw materials was confirmed by gas chromatography to determine the end point of the reaction. After the completion of the reaction, the reaction product was directly purified by vacuum distillation to obtain a colorless liquid as a target product. The obtained amount was 8.87 g (yield: 61.43%). The 1 H-NMR spectrum, IR spectrum and boiling point were the same as those obtained in Example 1.
【０００９】実施例３ １−メトキシ−２−ブタノールの合成：１００ｍｌ３径
フラスコにメタノール６．５ｍｌ，ＤＢＵ０．８４ｇ
（５．５ｍｍｏｌ），ヒドロキノンモノメチルエーテル
（ＭＱ）０．０１ｇを仕込み１，２−ブチレンオキシド
１０．０ｇ（１３７．８ｍｍｏｌ）を室温にて滴下し
た。その後７０℃で１２時間反応しガスクロマトグラフ
ィーにて原料消失の確認を行い反応の終点とした。反応
終了後、反応生成物は、そのまま減圧蒸留にて精製を行
い目的物無色液体を得た。得量１０．１７ｇ（収率７
０．４３％）１ Ｈ−ＮＭＲスペクトル、ＩＲスペクトル、沸点は実施
例１で得たものと同一であった。Example 3 Synthesis of 1-methoxy-2-butanol: 6.5 ml of methanol and 0.84 g of DBU were placed in a 100 ml three-diameter flask.
(5.5 mmol) and 0.01 g of hydroquinone monomethyl ether (MQ) were charged, and 10.0 g (137.8 mmol) of 1,2-butylene oxide was added dropwise at room temperature. Thereafter, the reaction was carried out at 70 ° C. for 12 hours, and the disappearance of the raw materials was confirmed by gas chromatography to determine the end point of the reaction. After the completion of the reaction, the reaction product was directly purified by distillation under reduced pressure to obtain a target colorless liquid. 10.17 g (yield 7)
0.43%) 1 H-NMR spectrum, IR spectrum and boiling point were the same as those obtained in Example 1.
【００１０】実施例４ １−メトキシ−２−ブタノールの合成：２０００ｍｌ４
径フラスコにメタノール２４４．４ｇ（７．６ｍｏ
ｌ），ＤＢＵ４２．２ｇ（０．２８ｍｏｌ），ヒドロキ
ノンモノメチルエーテル（ＭＱ）０．５ｇを仕込み１，
２−ブチレンオキシド５００．０ｇ（６．９ｍｏｌ），
を室温にて滴下した。その後４０℃〜７０℃で５時間反
応しガスクロクロマトグラフィーにて原料消失の確認を
行い反応の終点とした。反応終了後、反応生成物は、そ
のまま減圧蒸留にて精製を行い目的物たる無色液体を得
た。 得量 ６１２．１９ｇ（Ｙ８４．８％）１ Ｈ−ＮＭＲスペクトル、ＩＲスペクトル、沸点は実施
例１で得たものと同一であった。Example 4 Synthesis of 1-methoxy-2-butanol: 2000 ml 4
244.4g of methanol (7.6mo
l), 42.2 g (0.28 mol) of DBU and 0.5 g of hydroquinone monomethyl ether (MQ)
500.0 g (6.9 mol) of 2-butylene oxide,
Was added dropwise at room temperature. Thereafter, the reaction was carried out at 40 ° C. to 70 ° C. for 5 hours, and the disappearance of the raw materials was confirmed by gas chromatography to determine the end point of the reaction. After the completion of the reaction, the reaction product was directly purified by vacuum distillation to obtain a colorless liquid as a target product. The obtained amount was 612.19 g (Y84.8%). The 1 H-NMR spectrum, IR spectrum and boiling point were the same as those obtained in Example 1.
【００１１】実施例５ １−（２，２，２−トリフルオロエチル）オキシ−２−
ブタノールの合成：１００ｍｌ４径フラスコに２，２，
２−トリフルオロエタノール７．６ｇ（７５．７ｍｍｏ
ｌ），ＤＢＵ０．４２ｇ（２．８ｍｍｏｌ），ヒドロキ
ノンモノメチルエーテル（ＭＱ）０．００５ｇを仕込み
１，２−ブチレンオキシド５．０ｇ（６９．３ｍｍｏ
ｌ），を室温にて滴下した。その後４０℃〜６０℃で８
時間撹拌後ＤＢＵ１．０５ｇ，２，２，２−トリフルオ
ロエタノール２．０８ｇを添加し４０℃〜６０℃で６時
間反応した。反応生成物は、減圧蒸留にて精製を行い目
的物たる無色液体を得た。得量３．５９ｇ（収率３０．
２０％） ＩＲ スペクトル（ｎｅａｔ，ｃｍ−１）：３３９２，
２９４３，１４６６，１４１４，１２７９，１１５８，
９８１，８２Example 5 1- (2,2,2-trifluoroethyl) oxy-2-
Synthesis of butanol: 2,2 in a 100 ml 4-diameter flask
7.6 g of 2-trifluoroethanol (75.7 mmol
l), 0.42 g (2.8 mmol) of DBU and 0.005 g of hydroquinone monomethyl ether (MQ), and 5.0 g of 1,2-butylene oxide (69.3 mmol).
l) was added dropwise at room temperature. Then, at 40 ° C to 60 ° C, 8
After stirring for 1.0 hour, 1.05 g of DBU and 2.08 g of 2,2,2-trifluoroethanol were added and reacted at 40 ° C to 60 ° C for 6 hours. The reaction product was purified by distillation under reduced pressure to obtain a target substance as a colorless liquid. 3.59 g (yield 30.
20%) IR spectrum (neat, cm −1 ): 3392,
2943, 1466, 1414, 1279, 1158,
981,82
【００１２】実施例６ １−イソプロピルオキシ−２−ブタノール の合成：１
００ｍｌ３径フラスコにＤＢＵ１．１ｇ（０．００７２
ｍｏｌ），イソプロピルアルコール１６．７ｇ（０．２
８ｍｏｌ）ヒドロキノンモノメチルエーテル（ＭＱ）
０．０２ｇを仕込み１，２−ブチレンオキシド２０．０
ｇ（０．２８ｍｏｌ），を室温にて滴下した。その後７
０℃で３３．５時間反応しガスクロマトグラフィーにて
原料消失の確認を行い反応を終了した。反応終了後、反
応生成物は、そのまま減圧蒸留にて精製を行い目的物
６．６４ｇ（Ｙ１８．１１％）無色液体を得た。１ Ｈ−ＮＭＲスペクトル（ＣＤＣｌ３，ｐｐｍ）：０．
９６（ｔ３Ｈ），１．１７（ｄ６Ｈ），１．４６〜１．
５０（ｍ２Ｈ），２．４４（ｄ１Ｈ），３．２２（ｔ１
Ｈ），３．４５〜３．４８（ｍ１Ｈ），３．６０〜３．
６２（ｍ２Ｈ） ＩＲ スペクトル（ｎｅａｔ，ｃｍ−１：３４３６，２
９７２，２８７８，１４６６，１３８１，１１３１，１
０８６，９１９Example 6 Synthesis of 1-isopropyloxy-2-butanol: 1
In a 00 ml 3-diameter flask, 1.1 g of DBU (0.0072
mol), 16.7 g of isopropyl alcohol (0.2
8 mol) hydroquinone monomethyl ether (MQ)
0.02 g and 1,2-butylene oxide 20.0
g (0.28 mol) was added dropwise at room temperature. Then 7
The reaction was carried out at 0 ° C. for 33.5 hours, and the disappearance of the raw materials was confirmed by gas chromatography, and the reaction was completed. After the completion of the reaction, the reaction product was directly purified by distillation under reduced pressure to obtain 6.64 g (Y 18.11%) of a target substance as a colorless liquid. 1 H-NMR spectrum (CDCl 3 , ppm): 0.1.
96 (t3H), 1.17 (d6H), 1.46-1.
50 (m2H), 2.44 (d1H), 3.22 (t1
H), 3.45-3.48 (m1H), 3.60-3.
62 (m2H) IR spectrum (neat, cm -1 : 3436,2
972,2878,1466,1381,1131,1
086,919
【００１３】実施例７ １−ベンジルオキシ−２−ブタノール の合成：３００
ｍｌ４径フラスコにＤＢＵ１．３ｇ（０．００８５ｍｏ
ｌ），ベンジルアルコール２３．６ｍｌ（０．２３ｍｏ
ｌ）ヒドロキノンモノメチルエーテル（ＭＱ）０．０２
ｇを仕込み１，２−ブチレンオキシド１５．０ｇ（０．
２３ｍｏｌ），を室温にて滴下した。その後６０℃で１
０時間反応しガスクロマトグラフィーにて原料消失の確
認を行い反応の終点とした。反応終了後、反応生成物
は、そのまま減圧蒸留にて精製を行い目的物たる無色液
体を得た。 得量２６．２ｇ（収率６２．１％）１ Ｈ−ＮＭＲスペクトル（ＣＤＣｌ３，ｐｐｍ）：０．
９６（ｔ３Ｈ），１．４７〜１．５１（ｍ２Ｈ），２．
２８（ｄ１Ｈ），３．３４（ｔ１Ｈ），３．５０〜３．
５３（ｍ１Ｈ），３．７３〜３．７４（ｍ１Ｈ），４．
５６（ｓ２Ｈ），７．２５〜７．３５（ｍ５Ｈ） ＩＲ スペクトル（ｎｅａｔ，ｃｍ−１）：３４３６，
２９３２，２８７７，１９５２，１８７５，１８１１，
１６０５，１４９７，１４５５，１３６５，１０９９，
７３８，６９９Example 7 Synthesis of 1-benzyloxy-2-butanol: 300
1.3 g of DBU (0.0085 mol)
l), 23.6 ml of benzyl alcohol (0.23 mol
l) Hydroquinone monomethyl ether (MQ) 0.02
g, and 15.0 g of 1,2-butylene oxide (0.
23 mol) was added dropwise at room temperature. Then at 60 ° C for 1
The reaction was carried out for 0 hour, and the disappearance of the raw materials was confirmed by gas chromatography, and the reaction was regarded as the end point. After the completion of the reaction, the reaction product was directly purified by vacuum distillation to obtain a colorless liquid as a target product. 26.2 g (yield 62.1%) 1 H-NMR spectrum (CDCl 3 , ppm): 0.2.
96 (t3H), 1.47 to 1.51 (m2H), 2.
28 (d1H), 3.34 (t1H), 3.50-3.
53 (m1H), 3.73 to 3.74 (m1H), 4.
56 (s2H), 7.25 to 7.35 (m5H) IR spectrum (neat, cm -1 ): 3436,
2932, 2877, 1952, 1875, 1811,
1605, 1497, 1455, 1365, 1099,
738,699
【００１４】実施例８ １−メトキシ−２−ブタノールの合成：１００ｍｌ４径
フラスコに，メタノール４．９ｇ（０．１５ｍｏｌ），
ピリジン２．２ｇ（０．０２８ｍｏｌ）ヒドロキノンモ
ノメチルエーテル（ＭＱ）０．０１ｇを仕込み１，２−
ブチレンオキシド１０．０ｇ（０．１４ｍｏｌ）を室温
にて滴下した。その後５０℃〜６０℃で１８時間撹拌後
ピリジン１．１ｇを添加。６０℃にて６時間反応しガス
クロマトグラフィーにて原料消失の確認を行い反応の終
点とした。反応終了後、反応生成物は、そのまま減圧蒸
留にて精製を行い目的物たる無色液体を得た。 得量
５．７５ｇ（収率３９．８２％）１ Ｈ−ＮＭＲスペクトル、ＩＲ スペクトル、沸点は実
施例１で得たものと同一であった。Example 8 Synthesis of 1-methoxy-2-butanol: 4.9 g (0.15 mol) of methanol was placed in a 100-ml 4-diameter flask.
2.2 g (0.028 mol) of pyridine and 0.01 g of hydroquinone monomethyl ether (MQ) were charged and 1,2-
10.0 g (0.14 mol) of butylene oxide was added dropwise at room temperature. After stirring at 50 ° C to 60 ° C for 18 hours, 1.1 g of pyridine was added. The reaction was carried out at 60 ° C. for 6 hours, and the disappearance of the raw materials was confirmed by gas chromatography, which was regarded as the end point of the reaction. After the completion of the reaction, the reaction product was directly purified by vacuum distillation to obtain a colorless liquid as a target product. The obtained amount was 5.75 g (yield: 39.82%). The 1 H-NMR spectrum, IR spectrum, and boiling point were the same as those obtained in Example 1.
【００１５】実施例９ １−メトキシ−２−ブタノールの合成：１００ｍｌ４径
フラスコに，メタノール４．９ｇ（０．１５ｍｏｌ），
２，６−ルチジン１．４９ｇ（０．０１４ｍｏｌ）ヒド
ロキノンモノメチルエーテル（ＭＱ）０．０１ｇを仕込
み１，２−ブチレンオキシド１０．０ｇ（０．１４ｍｏ
ｌ），を室温にて滴下した。その後５０℃〜６０℃にて
２８時間撹拌した。目的物を２８．３６％の収率で得
た。Example 9 Synthesis of 1-methoxy-2-butanol: 4.9 g (0.15 mol) of methanol was placed in a 100-ml 4-diameter flask.
1.49 g (0.014 mol) of 2,6-lutidine and 0.01 g of hydroquinone monomethyl ether (MQ) were charged and 10.0 g of 1,2-butylene oxide (0.14 mol) was added.
l) was added dropwise at room temperature. Thereafter, the mixture was stirred at 50 ° C to 60 ° C for 28 hours. The desired product was obtained in a yield of 28.36%.
【００１６】実施例１０ １−メトキシ−２−ブタノールの合成：１００ｍｌ４径
フラスコに，メタノール８．９ｇ（０．２８ｍｏｌ），
トリエチルアミン１．１ｇ（０．０１１ｍｏｌ）ヒドロ
キノンモノメチルエーテル（ＭＱ）０．０２ｇを仕込み
１，２−ブチレンオキシド２０．０ｇ（０．２８ｍｏ
ｌ），を室温にて滴下した。その後６８℃で１１時間反
応しガスクロマトグラフィーにて原料消失の確認を行い
反応の終点とした。反応終了後、反応生成物は、そのま
ま減圧蒸留にて精製を行い目的物たる無色液体を得た。
得量２１．８６ｇ（Ｙ７５．６７％）１ Ｈ−ＮＭＲスペクトル、ＩＲスペクトル、沸点は実施
例でえたものと同一であった。Example 10 Synthesis of 1-methoxy-2-butanol: In a 100 ml 4-diameter flask, 8.9 g (0.28 mol) of methanol,
Triethylamine (1.1 g, 0.011 mol) and hydroquinone monomethyl ether (MQ) (0.02 g) were charged, and 1,2-butylene oxide (20.0 g, 0.28 mol) was added.
l) was added dropwise at room temperature. Thereafter, the reaction was carried out at 68 ° C. for 11 hours, and the disappearance of the raw materials was confirmed by gas chromatography, which was regarded as the end point of the reaction. After the completion of the reaction, the reaction product was directly purified by vacuum distillation to obtain a colorless liquid as a target product.
The obtained amount was 21.86 g (Y75.67%). The 1 H-NMR spectrum, IR spectrum and boiling point were the same as those obtained in the examples.
【００１７】実施例１１ （Ｒ）−１−メトキシ−２−オクタノール の合成：３
０ｍｌナスフラスコに，メタノール０．２６ｇ（８．１
ｍｍｏｌ），ＤＢＵ０．０４７ｇ（０．３１ｍｍｏｌ）
ヒドロキノンモノメチルエーテル（ＭＱ）少量を仕込み
（Ｒ）−１，２−エポキシオクタン１．０ｇ（７．８ｍ
ｍｏｌ），を室温にて滴下。その後４０℃〜８０℃で２
８時間反応しガスクロマトグラフィーにて原料消失の確
認を行い反応の終点とした。反応終了後、反応生成物
は、そのまま減圧蒸留にて精製を行い目的物０．１６ｇ
（Ｙ１３．３３％）無色液体を得た。１ Ｈ−ＮＭＲスペクトル（ＣＤＣｌ３，ｐｐｍ）：０．
８７〜０．８８（ｍ３Ｈ），１．２９〜１．４４（ｍ１
０Ｈ），２．２３（ｄ１Ｈ），３．２３（ｔ１Ｈ），
３．３９〜３．４２（ｍ４Ｈ），３．７６〜３．７７
（ｍ１Ｈ） ＩＲ スペクトル（ｎｅａｔ，ｃｍ−１）：３４３６，
２９２７，２８５８，１６４１，１４６０，１３７９，
１１９７，１１１６，８９４ 比旋光度［α］２０／Ｄ−４．７７（Ｃ２．０３０ ｉ
ｎ ＣＨＣｌ３）Example 11 Synthesis of (R) -1-methoxy-2-octanol: 3
In a 0 ml eggplant flask, 0.26 g of methanol (8.1
mmol), 0.047 g (0.31 mmol) of DBU
A small amount of hydroquinone monomethyl ether (MQ) was charged and 1.0 g of (R) -1,2-epoxyoctane (7.8 m
mol), at room temperature. Then at 40 ° C to 80 ° C, 2
The reaction was carried out for 8 hours, and the disappearance of the raw materials was confirmed by gas chromatography to determine the end point of the reaction. After completion of the reaction, the reaction product is directly purified by distillation under reduced pressure to obtain 0.16 g of the desired product
(Y 13.33%) A colorless liquid was obtained. 1 H-NMR spectrum (CDCl 3 , ppm): 0.1.
87 to 0.88 (m3H), 1.29 to 1.44 (m1
0H), 2.23 (d1H), 3.23 (t1H),
3.39 to 3.42 (m4H), 3.76 to 3.77
(M1H) IR spectrum (neat, cm -1 ): 3436,
2927, 2858, 1641, 1460, 1379,
1197, 1116, 894 Specific rotation [α] 20 / D −4.77 (C2.030 i
n CHCl 3 )
【００１８】実施例１２ １００ｍｌ４径フラスコに，メタノール８．９ｇ（０．
２８ｍｏｌ），（−）−Ｓｐａｒｔｅｉｎｅ ２．６ｇ
（０．０１１ｍｏｌ）ヒドロキノンモノメチルエーテル
（ＭＱ）０．０２ｇを仕込み１，２−ブチレンオキシド
２０．０ｇ（０．２８ｍｏｌ），を室温にて滴下。その
後６５℃〜７５℃で３３時間反応しガスクロマトグラフ
ィーにて原料消失の確認を行い反応の終点とした。反応
終了後、反応生成物は、そのまま減圧蒸留にて精製を行
い目的物３．６０ｇ（Ｙ１２．４６％）無色液体を得
た。１ Ｈ−ＮＭＲスペクトル（ＣＤＣｌ３，ｐｐｍ） ０．９７（ｔ３Ｈ），１．４６〜１．５０（ｍ２Ｈ），
２．２６（ｄ１Ｈ），３．２４（ｔ１Ｈ），３．３９〜
３．４３（ｍ４Ｈ），３．６９〜３．７０（ｍ１Ｈ） ＩＲ スペクトル（ｎｅａｔ，ｃｍ−１） ３４３６，２９６５，２９６７，２８８１，１４６１，
１１１０，９２０，５６１Example 12 In a 100 ml four-diameter flask, 8.9 g of methanol (0.
28 mol), (-)-Spartine 2.6 g
(0.011 mol) Hydroquinone monomethyl ether (MQ) 0.02 g was charged, and 1,2-butylene oxide 20.0 g (0.28 mol) was added dropwise at room temperature. Thereafter, the reaction was carried out at 65 ° C. to 75 ° C. for 33 hours, and the disappearance of the raw materials was confirmed by gas chromatography to determine the end point of the reaction. After the completion of the reaction, the reaction product was directly purified by distillation under reduced pressure to obtain 3.60 g (Y12.46%) of a target substance as a colorless liquid. 1 H-NMR spectrum (CDCl 3, ppm) 0.97 ( t3H), 1.46~1.50 (m2H),
2.26 (d1H), 3.24 (t1H), 3.39-
3.43 (m4H), 3.69 to 3.70 (m1H) IR spectrum (neat, cm -1 ) 3436, 2965, 2967, 2881, 1461,
1110,920,561
【００１９】実施例１３ １００ｍｌ４径フラスコに，メタノール１．５６ｇ（４
８．７ｍｍｏｌ），Ｒ−（＋）−Ｎ，Ｎ−ジメチル−１
−フェロセニルエチルアミン０．５ｇ（１．９ｍｍｏ
ｌ）ヒドロキノンモノメチルエーテル（ＭＱ）０．０２
ｇを仕込み１，２−ブチレンオキシド３．５ｇ（４８．
５ｍｍｏｌ），を室温にて滴下。その後５５℃〜６５℃
で１１時間反応しガスクロマトグラフィーにて原料消失
の確認を行い反応を終了した。反応終了後、反応生成物
は、そのまま減圧蒸留にて精製を行い目的物１．６８ｇ
（Ｙ３３．２％）無色液体を得た。１ Ｈ−ＮＭＲスペクトル（ＣＤＣｌ３，ｐｐｍ） ０．９７（ｔ３Ｈ），１．４６〜１．５０（ｍ２Ｈ），
２．２６（ｄ１Ｈ），３．２４（ｔ１Ｈ），３．３９〜
３．４３（ｍ４Ｈ），３．６９〜３．７０（ｍ１Ｈ） ＩＲ スペクトル（ｎｅａｔ，ｃｍ−１） ３４３６，２９６５，２９６７，２８８１，１４６１，
１１１０，９２０，５６１Example 13 1.56 g of methanol (4
8.7 mmol), R-(+)-N, N-dimethyl-1
0.5 g of ferrocenylethylamine (1.9 mmol)
l) Hydroquinone monomethyl ether (MQ) 0.02
g and 3.5 g of 1,2-butylene oxide (48.
5 mmol) at room temperature. Then 55 ° C to 65 ° C
And the reaction was terminated by confirming the disappearance of the raw materials by gas chromatography. After completion of the reaction, the reaction product is purified by distillation under reduced pressure as it is to obtain 1.68 g of the target product.
(Y33.2%) a colorless liquid was obtained. 1 H-NMR spectrum (CDCl 3, ppm) 0.97 ( t3H), 1.46~1.50 (m2H),
2.26 (d1H), 3.24 (t1H), 3.39-
3.43 (m4H), 3.69 to 3.70 (m1H) IR spectrum (neat, cm -1 ) 3436, 2965, 2967, 2881, 1461,
1110,920,561
【００２０】実施例１４ シクロヘキセンオキシド９８ｍｇ（１ｍｍｏｌ）にメタ
ノール（１２μＬ，３ｍｍｏｌ）とＤＢＵ（１８３μ
Ｌ，１．３ｍｍｏｌ）を加え、アセトニトリル２ｍｌの
混合溶液とした後、６０℃、８ｋｂａｒ加圧下で３日間
反応させた。反応終了後、２Ｎ−ＨＣ１を加えジエチル
エーテルで抽出した後、水、飽和食塩水で洗浄し、Ｎａ
２ＳＯ４で乾燥した。濃縮後、シリカゲル−カラムクロ
マトグラフィー（ヘキサン：酢酸エチル＝４：１）で精
製し、目的物を油状物質（４６ｍｇ）として得た。１ Ｈ−ＮＭＲスペクトル（ＣＤＣｌ３，ｐｐｍ） ３．４０（ｓ３Ｈ）０Ｍｅ ＩＲ スペクトル（ｎｅａｔ，ｃｍ−１） ３４４１，２９３４，２８６３，１７４０，１４５３，
１３７９，１２３５，１１９０，１１０１，９９７，９
１２，８４７，Example 14 To 98 mg (1 mmol) of cyclohexene oxide was added methanol (12 μL, 3 mmol) and DBU (183 μL).
L, 1.3 mmol) to give a mixed solution of 2 ml of acetonitrile, followed by a reaction at 60 ° C. under a pressure of 8 kbar for 3 days. After completion of the reaction, 2N-HC1 was added and extracted with diethyl ether, washed with water and saturated saline,
Dried over 2 SO 4 . After concentration, the residue was purified by silica gel-column chromatography (hexane: ethyl acetate = 4: 1) to obtain the desired product as an oil (46 mg). 1 H-NMR spectrum (CDCl 3 , ppm) 3.40 (s 3 H) 0 Me IR spectrum (neat, cm −1 ) 3441, 934, 2863, 1740, 1453,
1379, 1235, 1190, 1101, 997, 9
12,847,
【００２１】参考例 １−メトキシ−２−ブタノールの合成：１００ｍｌ３径
フラスコにＤＢＵ０．２１ｇ（１．４ｍｍｏｌ），メタ
ノール５ｍｌを仕込み１，２−ブチレンオキシド５．０
ｇ（９．３ｍｍｏｌ），を室温にて滴下した。その後４
０〜５０℃で６時間反応し、ガスクロマトグラフィーに
て目的生成物の生成を調べたが、わずかに確認できたに
過ぎなかった。Reference Example Synthesis of 1-methoxy-2-butanol: A 100-ml 3-diameter flask was charged with 0.21 g (1.4 mmol) of DBU and 5 ml of methanol, and 5.0 of 1,2-butylene oxide was added.
g (9.3 mmol) was added dropwise at room temperature. Then 4
The reaction was carried out at 0 to 50 ° C. for 6 hours, and the production of the target product was examined by gas chromatography, but it was only slightly confirmed.
Claims (7)
エポキシ化合物を反応させることを特徴とするエポキシ
化合物開環方法An epoxy compound ring opening method comprising reacting an alcohol with an epoxy compound in the presence of a tertiary amine.
て、エポキシ化合物が１，２−ブチレンオキシドである
エポキシ化合物開環方法2. The method according to claim 1, wherein the epoxy compound is 1,2-butylene oxide.
て、エポキシ化合物が１，２−ブチレンオキシドであ
り、アルコール類が 第一級低級アルコールであるエポ
キシ化合物開環方法3. The method according to claim 1, wherein the epoxy compound is 1,2-butylene oxide and the alcohol is a primary lower alcohol.
とを反応させ、エポキシ環を開環するに際し、１，８−
ジアザビシクロ〔５，４，０〕ウンデセン−７の存在下
に行うエポキシ化合物開環方法4. The reaction of 1,2-butylene oxide with an alcohol to open the epoxy ring,
Method for ring-opening epoxy compound in the presence of diazabicyclo [5,4,0] undecene-7
ールとを１，８−ジアザビシクロ〔５，４，０〕ウンデ
セン−７の存在下に反応させ、１−メトキシ−２−ヒド
ロキシブタンを得ることを特徴とする１−メトキシ−２
−ヒドロキシブタンの製造方法5. A method of reacting 1,2-butylene oxide and methyl alcohol in the presence of 1,8-diazabicyclo [5,4,0] undecene-7 to obtain 1-methoxy-2-hydroxybutane. Characterized 1-methoxy-2
-Method for producing hydroxybutane
ールとを１，８−ジアザビシクロ〔５，４，０〕ウンデ
セン−７の存在下に反応させ、１−メトキシ−２−ヒド
ロキシブタンを得るに際し、ヒドロキノンモノメチルエ
ーテルを添加することを特徴とする１−メトキシ−２−
ヒドロキシブタンの製造方法6. A reaction between 1,2-butylene oxide and methyl alcohol in the presence of 1,8-diazabicyclo [5,4,0] undecene-7 to obtain 1-methoxy-2-hydroxybutane. 1-methoxy-2-characterized by adding hydroquinone monomethyl ether
Method for producing hydroxybutane
アルコール１モル以上とを１，８−ジアザビシクロ
〔５，４，０〕ウンデセン−７の存在下に反応させ、１
−メトキシ−２−ヒドロキシブタンを得るに際し、１，
８−ジアザビシクロ〔５，４，０〕ウンデセン−７を
０．０４モル以上使用することを特徴とする１−メトキ
シ−２−ヒドロキシブタンの製造方法 【０００１】7. A reaction of 1 mol of 1,2-butylene oxide and 1 mol or more of methyl alcohol in the presence of 1,8-diazabicyclo [5,4,0] undecene-7 to obtain 1
In obtaining methoxy-2-hydroxybutane,
[0001] A process for producing 1-methoxy-2-hydroxybutane, comprising using 0.04 mol or more of 8-diazabicyclo [5,4,0] undecene-7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8359666A JPH10175902A (en) | 1996-12-18 | 1996-12-18 | Ring opening of epoxy compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8359666A JPH10175902A (en) | 1996-12-18 | 1996-12-18 | Ring opening of epoxy compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10175902A true JPH10175902A (en) | 1998-06-30 |
Family
ID=18465674
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8359666A Pending JPH10175902A (en) | 1996-12-18 | 1996-12-18 | Ring opening of epoxy compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10175902A (en) |
-
1996
- 1996-12-18 JP JP8359666A patent/JPH10175902A/en active Pending
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