JPS64376B2 - - Google Patents
Info
- Publication number
- JPS64376B2 JPS64376B2 JP58200680A JP20068083A JPS64376B2 JP S64376 B2 JPS64376 B2 JP S64376B2 JP 58200680 A JP58200680 A JP 58200680A JP 20068083 A JP20068083 A JP 20068083A JP S64376 B2 JPS64376 B2 JP S64376B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- following formula
- magnetic resonance
- nuclear magnetic
- compound
- 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.)
- Expired
Links
- 150000001875 compounds Chemical class 0.000 claims description 9
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims 1
- 150000001241 acetals Chemical class 0.000 description 8
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 7
- 239000007858 starting material Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- -1 alkali metal salt Chemical class 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001728 carbonyl compounds Chemical class 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- BMTAFVWTTFSTOG-UHFFFAOYSA-N Butylate Chemical compound CCSC(=O)N(CC(C)C)CC(C)C BMTAFVWTTFSTOG-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- ZKQFHRVKCYFVCN-UHFFFAOYSA-N ethoxyethane;hexane Chemical compound CCOCC.CCCCCC ZKQFHRVKCYFVCN-UHFFFAOYSA-N 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QPXQVNXSQCRWEV-UHFFFAOYSA-N methoxymethylsulfanylbenzene Chemical compound COCSC1=CC=CC=C1 QPXQVNXSQCRWEV-UHFFFAOYSA-N 0.000 description 1
- MZIVRTQIEKRAPI-UHFFFAOYSA-N methoxymethylsulfonylbenzene Chemical compound COCS(=O)(=O)C1=CC=CC=C1 MZIVRTQIEKRAPI-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
本発明はアセタールの新規な合成法に関する。
更に詳細には、下記式（）または（）で表わ
される化合物をスルホン酸の存在下でR1OHと作
用させることを特徴とする下記式（）で表わさ
れるアセタールの合成法に関する。
但し、上記式（），（）および（）におい
て、Ｒはそれぞれ置換基を有していてもよい、ア
ルキル基、アルケニル基、アリール基およびアラ
ルキル基より選ばれる基を表わし、phはフエニ
ル基、R1は低級アルキル基をそれぞれ表わす。
従来アセタールの合成法は数多く知られている
が、本発明によれば、下記式（）で表わされる
ように、上記式（）または（）の化合物に、
例えばＰ―トルエンスルホン酸（Ｐ―TSOH）
のごとき緩和な酸の存在下でアルコールを作用さ
せると、短時間において好収率でアセタールを生
成する。
本発明に用いられる上記（），（）で表わさ
れる化合物は、それぞれ次のような既知の方法で
容易に合成することができる。
即ち、下記式で表わされるように、例えばそれ
ぞれ公知のメトキシフエニルチオメタン、メトキ
シフエニルスルホニルメタンにブチル化リチウム
を作用させてアルカリ金属塩をつくり、これをア
ルキルハライドの如き有機ハライド又はカルボニ
ル化合物と縮合させることによつて容易につくら
れる。下記式においてR2は、上記式（）のＲ
と同様に定義される基である。
上記のように本発明は、有機ハライドまたはカ
ルボニル化合物を出発物質としてＣ―Ｃ結合の生
成による炭素数が１個増加したアセタールの一般
的合成法を提供するものである。
本発明は反応式（）に示されるように、原料
物質である式（）または式（）の化合物を少
量のスルホン酸の存在下でアルコールに溶解し短
時間還流すればよい。
アルコール（R1OH）としては、低級アルキル
脂肪族アルコールがよく、特にメタノールが、還
流温度が低く、反応が最も容易である点で最も好
ましい。またスルホン酸としてはベンゼンスルホ
ン酸、Ｐ―トルエンスルホン酸などが一般的に使
用できる。
以下実施例によつて本発明を説明する。
実施例 １
下記式で示される原料化合物(a)100mg（0.41m
mol）を乾燥メタノールに溶解し、触媒量のＰ―
トルエンスルホン酸（Ｐ―TSOH）を加え、２
時間還流した。水で稀釈した後、ベンベンで抽出
し、重曹水で洗浄後、カラムクロマト（シリカゲ
ル、ヘキサン―エーテル＝50：１（容量））で精製
した。
下記式においてphはフエニル基を表わす（以
下の例において同じ）。
実施例 ２
下記式で示される原料化合物(b)〜(f)を用いて、
実施例１と同様にして対応するアセタールを製造
した。
上記原料化合物(f)のように、フエニルチオ体の
場合においてβ―ヒドロキシ化合物では、転位反
応を伴なつたアセタールを生ずる。しかしなが
ら、原料化合物(d)，(e)のようにフエニルスルホニ
ル体の場合は正常のアセタールを生ずる。
上記実施例１および実施例２の原料化合物およ
び生成物の核磁気共鳴スペクトルを第１図〜第９
図に示した。なお、測定は(a)，(b)，(c)，及び(B)は
四塩化炭素、(d)は重クロロホルムをそれぞれ溶媒
とし、(e)，(f)，(D)及び(F)は無溶媒にてTMS基準
で行なつた。
また、実施例１および実施例２の原料化合物お
よび生成物の薄層クロマトによるRf値を第１表
に示した。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for the synthesis of acetals.
More specifically, the present invention relates to a method for synthesizing an acetal represented by the following formula (), which is characterized by reacting a compound represented by the following formula () or () with R 1 OH in the presence of a sulfonic acid. However, in the above formulas (), () and (), R represents a group selected from an alkyl group, an alkenyl group, an aryl group and an aralkyl group, each of which may have a substituent, and ph is a phenyl group, R 1 each represents a lower alkyl group. Many methods of synthesizing acetal have been known in the past, but according to the present invention, as represented by the following formula (), the compound of the above formula () or () is combined with
For example, P-toluenesulfonic acid (P-TSOH)
When alcohols are reacted in the presence of mild acids, such as alcohols, acetals are produced in good yields in a short time. The compounds represented by () and () above used in the present invention can be easily synthesized by the following known methods. That is, as shown in the following formula, for example, lithium butylate is reacted with known methoxyphenylthiomethane and methoxyphenylsulfonylmethane to prepare an alkali metal salt, which is then mixed with an organic halide such as an alkyl halide or a carbonyl compound. It is easily produced by condensation with In the following formula, R 2 is R in the above formula ()
This is a group defined in the same way as . As described above, the present invention provides a general method for synthesizing an acetal having an increased number of carbon atoms by one by forming a C--C bond using an organic halide or carbonyl compound as a starting material. In the present invention, as shown in reaction formula (), the raw material of formula () or the compound of formula () may be dissolved in alcohol in the presence of a small amount of sulfonic acid and refluxed for a short time. As the alcohol (R 1 OH), lower alkyl aliphatic alcohols are preferred, and methanol is particularly preferred since it has a low reflux temperature and is the easiest to react with. Furthermore, as the sulfonic acid, benzenesulfonic acid, P-toluenesulfonic acid, etc. can generally be used. The present invention will be explained below with reference to Examples. Example 1 100 mg (0.41 m
mol) in dry methanol and a catalytic amount of P-
Add toluenesulfonic acid (P-TSOH),
Refluxed for an hour. After diluting with water, the mixture was extracted with benben, washed with aqueous sodium bicarbonate, and purified by column chromatography (silica gel, hexane-ether = 50:1 (volume)). In the following formula, ph represents a phenyl group (the same applies in the following examples). Example 2 Using raw material compounds (b) to (f) shown by the following formulas,
The corresponding acetal was produced in the same manner as in Example 1. In the case of a phenylthio compound like the above-mentioned raw material compound (f), a β-hydroxy compound produces an acetal accompanied by a rearrangement reaction. However, in the case of phenylsulfonyl derivatives such as starting compounds (d) and (e), normal acetals are produced. The nuclear magnetic resonance spectra of the raw material compounds and products of Example 1 and Example 2 are shown in Figures 1 to 9.
Shown in the figure. The measurements were carried out using carbon tetrachloride for (a), (b), (c), and (B), and deuterated chloroform for (d), and (e), (f), (D), and (F). ) was performed without solvent using TMS standards. Table 1 also shows the Rf values of the raw material compounds and products of Example 1 and Example 2 as determined by thin layer chromatography. 【table】
第１図〜第６図は実施例１および実施例２に用
いた原料化合物ａ〜ｆのそれぞれの核磁気共鳴ス
ペクトルを示し、第７図〜第９図は上記実施例に
よつて得られた生成物Ｂ，Ｄ及びＦのそれぞれの
核磁気共鳴スペクトルを示す。
Figures 1 to 6 show the respective nuclear magnetic resonance spectra of the starting compounds a to f used in Example 1 and Example 2, and Figures 7 to 9 show the nuclear magnetic resonance spectra of the starting compounds a to f used in Example 1 and Example 2, and Figures 7 to 9 show the nuclear magnetic resonance spectra of the starting compounds a to f used in Example 1 and Example 2, and Figures 7 to 9 show the nuclear magnetic resonance spectra of the starting compounds a to f used in Example 1 and Example 2, and Figures 7 to 9 show the nuclear magnetic resonance spectra of the starting compounds a to f used in Example 1 and Example 2. The nuclear magnetic resonance spectra of each of products B, D and F are shown.
Claims (1)
物をスルホン酸の存在下でR1OHと作用させるこ
とを特徴とする下記式（）で表わされるアセタ
ールの合成法。 但し、上記式（），（）および（）におい
て、Ｒはそれぞれ置換基を有していてもよい、ア
ルキル基、アルケニル基、アリール基およびアラ
ルキル基より選ばれる基を表わし、phはフエニ
ル基、R1は低級アルキル基をそれぞれ表わす。[Scope of Claims] 1. A method for synthesizing an acetal represented by the following formula (), which comprises reacting a compound represented by the following formula () or () with R 1 OH in the presence of a sulfonic acid. However, in the above formulas (), () and (), R represents a group selected from an alkyl group, an alkenyl group, an aryl group and an aralkyl group, each of which may have a substituent, and ph is a phenyl group, R 1 each represents a lower alkyl group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58200680A JPS6092231A (en) | 1983-10-25 | 1983-10-25 | Synthetic method of acetal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58200680A JPS6092231A (en) | 1983-10-25 | 1983-10-25 | Synthetic method of acetal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6092231A JPS6092231A (en) | 1985-05-23 |
| JPS64376B2 true JPS64376B2 (en) | 1989-01-06 |
Family
ID=16428457
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58200680A Granted JPS6092231A (en) | 1983-10-25 | 1983-10-25 | Synthetic method of acetal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6092231A (en) |
-
1983
- 1983-10-25 JP JP58200680A patent/JPS6092231A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6092231A (en) | 1985-05-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5110987A (en) | Method of preparing sphingosine derivatives | |
| US5191069A (en) | Polyfunctional compounds containing α-diazo-β-keto ester units and sulfonate units | |
| US4107439A (en) | Process for preparing arylalkanoic acid derivatives | |
| JPS64376B2 (en) | ||
| JPH09509946A (en) | Method for producing monoacetal of hydroquinone | |
| US4443621A (en) | p-Nitrophenyl 3-bromo-2,2-diethoxy-propionate and synthetic utility therefor | |
| JP2718645B2 (en) | Benzoheterocyclic compound, method for producing the same and composition containing the same | |
| US4656309A (en) | Preparation of alpha-pivaloyl-substituted acetic acid esters | |
| US5194651A (en) | Tosylation of alcohols | |
| JPH06501021A (en) | Process for producing certain bis-azabicyclic anxiolytics and intermediates thereof | |
| JP2536516B2 (en) | Hydroxycyclopentanones | |
| Ollmann et al. | Convenient synthesis of primary benzhydrylamines | |
| JPS6350336B2 (en) | ||
| SU1038341A1 (en) | Process for preparing alpha-arylindolotrimethylecyanines | |
| JP3281916B2 (en) | Method for producing acetal compound and catalyst for the production reaction | |
| HU221419B1 (en) | Process for producing 1,3-dioxane compounds | |
| JPH02149538A (en) | Production of symmetric and asymmetric monoacetal of aromatic 1,2-diketone | |
| JPH11171812A (en) | Benzyl ether dendrimer compound | |
| JP3770678B2 (en) | Optically active alcohol and its carboxylic acid ester | |
| JPH03123768A (en) | Production of bisalkylsofonoxymethyl ethers or bisarylsulfonoxymethyl ethers | |
| JPS5883686A (en) | Production method of aminocyclopentane alkenoic acid | |
| JP3097273B2 (en) | Host functional material | |
| JPS6350340B2 (en) | ||
| JPH027583B2 (en) | ||
| JPS59167582A (en) | Manufacture of 5-substituted-3-furanic acid alkyl compounds |