JPH0146495B2 - - Google Patents
Info
- Publication number
- JPH0146495B2 JPH0146495B2 JP62254888A JP25488887A JPH0146495B2 JP H0146495 B2 JPH0146495 B2 JP H0146495B2 JP 62254888 A JP62254888 A JP 62254888A JP 25488887 A JP25488887 A JP 25488887A JP H0146495 B2 JPH0146495 B2 JP H0146495B2
- Authority
- JP
- Japan
- Prior art keywords
- acid ester
- triphenylphosphine
- reaction
- iodine
- present
- 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
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
本発明は脂肪族ヨウ化物の新規な製造法に関す
る。
脂肪族ヨウ化物は有機ハロゲン化物のひとつと
して、合成化学の重要な中間体であり、数多の合
成経路に介在するので、各種の合成法が開発され
て来たが、ここに完成した本発明により、その経
路は更に飛躍的に豊富な可能性を合成化学に与え
ることになつた。
即ち、本発明は、一般式Ｒ・Ａ（Ｒは飽和脂肪
族残基部位でＡと結合する有機基、Ａはスルホン
酸ハライド、スルフイン酸、スルフイン酸エステ
ル、チオスルホン酸エステル又はチオスルフイン
酸エステルを示す。）で示される化合物を、トリ
フエニルホスフイン及びヨウ素と反応させ、脂肪
族ヨウ化物Ｒ・Ｉを製造する方法である。
本発明は、通常、無水の状態で不活性ガス雰囲
気中、Ｒ・Ａなる硫黄を含有して成る官能基をも
つ脂肪族化合物と、トリフエニルホスフインと、
ヨウ素とを、適当な有機溶媒中混合して常温乃至
加熱反応させて実施する。有機溶媒は、充分に脱
水された、本発明反応の基質・試剤と反応せず、
これらを溶解するものが好ましく、そのような通
常のもののうち例えばベンゼン、シクロヘキサ
ン、ヘプタン、ジクロルメタンなどが好適であ
り、反応は通常それら反応溶媒の還流温度以下で
行われ、通常単離収率80％以上で定量的に成績体
が得られる。反応は例えばＡがスルフイン酸であ
る場合、Ｒ・SO2H＋3Ph3P＋I2→Ｒ・Ｉ＋2Ph3P
（Ｏ）＋Ph3P（Ｓ）＋HIの式に従うので、試剤をそ
の当量乃至若干過剰に使用するのが好ましい。こ
の反応で副生するトリフエニルホスフインオキシ
ド及びトリフエニルホスフインスルフイドは、適
宜還元して原料試剤トリフエニルホスフインとし
て回収再使用される。
尚基質の硫黄含有官能基が、チオスルホン酸エ
ステルである場合、エステルを与えるアルコール
類の脂肪族残基をR′で表わすと、反応式は次の
通りである。
Ｒ・SO2SR′＋4Ph3P＋I2→Ｒ・Ｉ＋R′・Ｉ＋
2Ph3P（Ｏ）＋2Ph3P（Ｓ）即ちR′・Ｉが副生する
から、R′をＲに等しく選ぶと効率は更に向上す
る。
Ｒで示される飽和脂肪族残基部位でＡと結合す
る有機基とは、例えばアルキル、アルアルキル、
及びそれらの、本発明反応試剤と反応することの
ない置換体をいう。以下に実施例を示す。数量を
示す％は重量％である。
実施例 １
ペンタスルフイン酸0.1mol（13.6ｇ）、トリフエ
ニルホスフイン0.33mol（86.5ｇ）、ヨウ素0.15mol
（38.1ｇ）を、よく乾燥したベンゼン200ｇに混
じ、窒素ガス雰囲気中、室温で２時間反応させ
た。ベンゼン100ｇを加えた後３回水洗し、硫酸
マグネシウムで脱水し、ベンゼンを留去、減圧蒸
留してヨウ化ペンチル18.8（収率95％）を得た。
実施例２及び３
実施例１と同様にして以下の結果を得た。
The present invention relates to a novel method for producing aliphatic iodides. As an organic halide, aliphatic iodide is an important intermediate in synthetic chemistry and intervenes in numerous synthetic routes, so various synthetic methods have been developed, but the present invention has been completed here. As a result, the route has opened up even more dramatically rich possibilities for synthetic chemistry. That is, the present invention is based on the general formula R.A (R is an organic group bonded to A at a saturated aliphatic residue site, A represents a sulfonic acid halide, a sulfinic acid, a sulfinic acid ester, a thiosulfonic acid ester, or a thiosulfinic acid ester) .) is reacted with triphenylphosphine and iodine to produce aliphatic iodide R.I. The present invention generally comprises an aliphatic compound having a sulfur-containing functional group, R.A., and triphenylphosphine in an inert gas atmosphere in an anhydrous state.
The reaction is carried out by mixing iodine and iodine in a suitable organic solvent and reacting at room temperature or heating. The organic solvent does not react with the substrate/reagent of the reaction of the present invention, which has been sufficiently dehydrated.
It is preferable to use a substance that can dissolve these substances, and among such common substances, for example, benzene, cyclohexane, heptane, dichloromethane, etc. are suitable.The reaction is usually carried out at a temperature below the reflux temperature of the reaction solvent, and the isolation yield is usually 80%. With the above steps, a quantitative score can be obtained. For example, when A is sulfinic acid, the reaction is R・SO 2 H + 3Ph 3 P + I 2 →R・I + 2Ph 3 P
Since the formula (O)+Ph 3 P(S)+HI is followed, it is preferable to use the reagent in an equivalent amount or in slight excess. Triphenylphosphine oxide and triphenylphosphine sulfide, which are by-produced in this reaction, are appropriately reduced and recovered and reused as the raw material reagent triphenylphosphine. When the sulfur-containing functional group of the substrate is a thiosulfonic acid ester, and the aliphatic residue of the alcohol that provides the ester is represented by R', the reaction formula is as follows. R・SO 2 SR′+4Ph 3 P+I 2 →R・I+R′・I+
Since 2Ph 3 P(O)+2Ph 3 P(S), that is, R'·I, is produced as a by-product, if R' is chosen to be equal to R, the efficiency is further improved. The organic group bonded to A at the saturated aliphatic residue site represented by R is, for example, alkyl, aralkyl,
and substituted products thereof that do not react with the reaction reagent of the present invention. Examples are shown below. The percentages indicating quantities are percentages by weight. Example 1 Pentasulfinic acid 0.1 mol (13.6 g), triphenylphosphine 0.33 mol (86.5 g), iodine 0.15 mol
(38.1 g) was mixed with 200 g of well-dried benzene and reacted for 2 hours at room temperature in a nitrogen gas atmosphere. After adding 100 g of benzene, the mixture was washed with water three times, dehydrated with magnesium sulfate, benzene was distilled off, and distilled under reduced pressure to obtain 18.8 g of pentyl iodide (yield: 95%). Examples 2 and 3 The following results were obtained in the same manner as in Example 1.
【表】
実施例 ４〜７
実施例１と同様にして以下の結果を得た。溶剤は
シクロヘキサンを用いた。[Table] Examples 4 to 7 The following results were obtained in the same manner as in Example 1. Cyclohexane was used as the solvent.
Claims (1)
と結合する有機基、Ａはスルホン酸ハライド、ス
ルフイン酸、スルフイン酸エステル、チオスルホ
ン酸エステル又はチオスルフイン酸エステルを示
す。）で示される化合物を、トリフエニルホスフ
イン及びヨウ素と反応させることを特徴とする、
脂肪族ヨウ化物Ｒ・Ｉ（Ｒは前記と同じ。）の製
法。1 General formula R・A (R is a saturated aliphatic residue site and A
The organic group bonded to A represents a sulfonic acid halide, a sulfinic acid, a sulfinic acid ester, a thiosulfonic acid ester, or a thiosulfinic acid ester. ) is reacted with triphenylphosphine and iodine,
A method for producing aliphatic iodide R.I (R is the same as above).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62254888A JPH0196142A (en) | 1981-03-02 | 1987-10-09 | Production of aliphatic iodide |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2950481A JPS57144230A (en) | 1981-03-02 | 1981-03-02 | Production of aliphatic iodide |
| JP62254888A JPH0196142A (en) | 1981-03-02 | 1987-10-09 | Production of aliphatic iodide |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2950481A Division JPS57144230A (en) | 1981-03-02 | 1981-03-02 | Production of aliphatic iodide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0196142A JPH0196142A (en) | 1989-04-14 |
| JPH0146495B2 true JPH0146495B2 (en) | 1989-10-09 |
Family
ID=26367713
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62254888A Granted JPH0196142A (en) | 1981-03-02 | 1987-10-09 | Production of aliphatic iodide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0196142A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2811131B2 (en) * | 1991-04-26 | 1998-10-15 | 三菱電機株式会社 | Wiring connection structure of semiconductor device and method of manufacturing the same |
| EP0558304B1 (en) * | 1992-02-28 | 2000-01-19 | STMicroelectronics, Inc. | Method of forming submicron contacts |
| JP4770202B2 (en) * | 2005-03-08 | 2011-09-14 | ダイキン工業株式会社 | Method for producing fluorine-containing halide |
-
1987
- 1987-10-09 JP JP62254888A patent/JPH0196142A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0196142A (en) | 1989-04-14 |
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