JPS6145996B2 - - Google Patents
Info
- Publication number
- JPS6145996B2 JPS6145996B2 JP8086779A JP8086779A JPS6145996B2 JP S6145996 B2 JPS6145996 B2 JP S6145996B2 JP 8086779 A JP8086779 A JP 8086779A JP 8086779 A JP8086779 A JP 8086779A JP S6145996 B2 JPS6145996 B2 JP S6145996B2
- Authority
- JP
- Japan
- Prior art keywords
- amine
- borane
- reaction
- dmf
- nabh
- 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
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 25
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 20
- 150000001412 amines Chemical class 0.000 claims description 13
- 229910000085 borane Inorganic materials 0.000 claims description 10
- -1 amine salts Chemical class 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- XHFGWHUWQXTGAT-UHFFFAOYSA-N dimethylamine hydrochloride Natural products CNC(C)C XHFGWHUWQXTGAT-UHFFFAOYSA-N 0.000 description 2
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JYHRLWMNMMXIHF-UHFFFAOYSA-N (tert-butylamino)boron Chemical compound [B]NC(C)(C)C JYHRLWMNMMXIHF-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- VDTVZBCTOQDZSH-UHFFFAOYSA-N borane N-ethylethanamine Chemical compound B.CCNCC VDTVZBCTOQDZSH-UHFFFAOYSA-N 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- YJROYUJAFGZMJA-UHFFFAOYSA-N boron;morpholine Chemical compound [B].C1COCCN1 YJROYUJAFGZMJA-UHFFFAOYSA-N 0.000 description 1
- VEWFZHAHZPVQES-UHFFFAOYSA-N boron;n,n-diethylethanamine Chemical compound [B].CCN(CC)CC VEWFZHAHZPVQES-UHFFFAOYSA-N 0.000 description 1
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000005055 short column chromatography Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
【発明の詳細な説明】
本発明はアミンボランの製法に関し、詳しくは
アミンの塩類とホウ素化合物を反応させてアミン
ボランを製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing amine borane, and more particularly to a method for producing amine borane by reacting amine salts with a boron compound.
従来、アミンボランを工業的に製造する方法と
して、アミンとジボランを反応させる方法が知ら
れているが、ジボランは有害な気体であり、また
無水状態の保持など取扱いが容易でなかつた。そ
こで、ジボランを使用しないアミンボランの製法
として、アミンと水素化ホウ素ナトリウムを水−
トルエン溶媒中で反応させる方法が試みられた
（西独公開特許第1618387号）が、この方法は収率
が低く、しかも反応の後処理が複雑で工業的な製
造法としては全く満足すべきものではなかつた。 Conventionally, a method of reacting an amine with diborane has been known as a method for industrially producing amine borane, but diborane is a harmful gas and is difficult to handle, such as maintaining an anhydrous state. Therefore, as a method for producing amine borane without using diborane, amine and sodium borohydride are mixed in water.
A method of reacting in a toluene solvent was attempted (West German Published Patent No. 1618387), but this method had a low yield and complicated post-treatment, making it completely unsatisfactory as an industrial production method. Ta.
本発明者は、この後者の方法について種々検討
し、反応溶媒として、テトラヒドロフラン、ジオ
キサン、エーテルその他を用いたときは、反応に
長時間を要し、しかも満足すべき収率で反応が進
行しないのに対し、ジメチルホルムアミドを溶媒
として使用したときは、緩和な条件下でも短時間
で収率よく反応が進行することを発見し、本発明
を完成した。 The present inventor conducted various studies on this latter method, and found that when tetrahydrofuran, dioxane, ether, etc. are used as the reaction solvent, the reaction takes a long time and does not proceed with a satisfactory yield. In contrast, they discovered that when dimethylformamide was used as a solvent, the reaction proceeded in a short time and with good yield even under mild conditions, and the present invention was completed.
すなわち、本発明はアミンの塩類と水素化ホウ
素ナトリウム（NaBH4）をジメチルホルムアミド
中で反応させることを特徴とするアミンボランの
製造方法である。 That is, the present invention is a method for producing amine borane, which is characterized by reacting an amine salt and sodium borohydride (NaBH 4 ) in dimethylformamide.
本発明で用いるアミンは、ｔ−ブチルアミン、
ジメチルアミン、ジエチルアミン、モルホリン、
トリエチルアミン等それらの対応するアミンボラ
ンが有用なものを言い、それらの塩類としては、
塩酸塩、臭化水素酸塩、ヨウ化水素酸塩等の無機
酸塩及び各種有機酸塩が挙げられるが、入手の容
易さ、反応性、反応の後処理の容易さを考慮すれ
ば塩酸塩が最も好ましく、特に他の塩を用いる必
要はない。 The amine used in the present invention is t-butylamine,
dimethylamine, diethylamine, morpholine,
The corresponding amineboranes such as triethylamine are useful, and their salts include:
Examples include inorganic acid salts such as hydrochloride, hydrobromide, and hydroiodide, and various organic acid salts, but considering ease of availability, reactivity, and ease of post-treatment of the reaction, hydrochloride is most preferred, and there is no need to use other salts.
反応は、アミンの塩類とNaBH4をDMF中で氷
冷下ないし室温にて行なう。アミンの塩類を
DMFに溶解もしくは懸濁させておき、これに
NaBH4を粉末のまま加えてもよいが、NaBH4を
DMFに加えたものを滴下させたほうがよりよい
結果が得られる。アミンの塩類とNaBH4はほぼ
等モルか一方をやや過剰に用いる。反応時間は
0.5〜1.5時間を要し、それ以下の短時間例えば10
分間ぐらいの反応時間では、反応が完全には進行
しない場合がある。反応後はDMFを溜去し、ベ
ンゼン、ジクロルメタン等、生成したアミンボラ
ンを溶解する有機溶媒を加えれば、反応により生
成した塩及び微量の未反応物を不溶物として分離
することができる。有機溶媒を溜去して得られる
アミンボランはほぼ純品であるが、さらに蒸溜、
再結晶あるいはカラムクロマトグラフイーで精製
することができる。 The reaction is carried out between the amine salt and NaBH 4 in DMF under ice-cooling or at room temperature. amine salts
Dissolve or suspend in DMF and add
NaBH 4 may be added as a powder, but NaBH 4
You will get better results if you add it to DMF and drip it. The amine salt and NaBH 4 are used in approximately equimolar amounts, or one is used in slightly excess. The reaction time is
It takes 0.5-1.5 hours, less short time e.g. 10
The reaction may not proceed completely with a reaction time of about one minute. After the reaction, by distilling off DMF and adding an organic solvent that dissolves the produced amine borane, such as benzene or dichloromethane, the salt produced by the reaction and trace amounts of unreacted substances can be separated as insoluble matter. The amine borane obtained by distilling off the organic solvent is almost pure, but it can be further distilled and
It can be purified by recrystallization or column chromatography.
本発明によれば、安価な原料より、簡単な操作
でアミンボランを得ることが可能であるし、特別
な装置を必要としない。また、溶媒として用いる
DMFも蒸溜によつて回収し再利用できるので、
無駄になるものが全くなく、しかも無水状態の保
持や、引火性等の注意など必要でないため、工業
的なアミンボランの製法としてきわめて好ましい
ものである。 According to the present invention, amine borane can be obtained from inexpensive raw materials through simple operations, and no special equipment is required. Also used as a solvent
DMF can also be recovered and reused through distillation, so
Since nothing is wasted and there is no need to maintain an anhydrous state or take precautions against flammability, this is an extremely preferable method for industrially producing amine borane.
以下、実施例を挙げて具体的に説明する。 Hereinafter, this will be explained in detail by giving examples.
実施例 １
ジメチルアミン塩酸塩11ミリモル（896mg）を
DMF9mlに加え、これにNaBH410ミリモル（370
mg）をDMF9mlに加えたものを氷冷下滴下した。
室温にて1.5時間撹拌後、DMFを減圧下溜去し、
残渣にベンゼン100mlを加え、不溶物を去し
た。Example 1 11 mmol (896 mg) of dimethylamine hydrochloride
In addition to 9 ml of DMF, add 10 mmol of NaBH 4 (370
mg) in 9 ml of DMF was added dropwise under ice-cooling.
After stirring at room temperature for 1.5 hours, DMF was distilled off under reduced pressure.
100 ml of benzene was added to the residue to remove insoluble matter.
ベンゼンを溜去し、残渣を短かいカラムクロマ
トグラフイー（SiO220ｇ、CH2Cl2で流出）で精
製してジメチルアミンボラン510mgを得た。mp35
〜35.5℃
実施例 ２
実施例１のジメチルアミン塩酸塩にかえ、ｔ−
ブチルアミン、ジエチルアミン、モルホリン、ト
リエチルアミンそれぞれの塩酸塩11ミリモルを用
いて、それぞれ実施例１と同様の操作を行なつ
た。得られた化合物、反応時間（室温撹拌時間）
収量は以下のとおりであつた。 The benzene was distilled off and the residue was purified by short column chromatography (20 g of SiO 2 , eluting with CH 2 Cl 2 ) to give 510 mg of dimethylamine borane. mp35
~35.5°C Example 2 Instead of dimethylamine hydrochloride in Example 1, t-
The same operations as in Example 1 were carried out using 11 mmol of each of the hydrochlorides of butylamine, diethylamine, morpholine, and triethylamine. Obtained compound, reaction time (room temperature stirring time)
The yield was as follows.
(1) ｔ−ブチルアミンボランmp92〜94℃（分
解）、10分間、490mg
(2) ジエチルアミンボラン油状〔IR（cm-1）：
3225、3000〜2900、2410〜2290、1180〕、10分
間、570mg
(3) モルホリンボランmp95〜96℃、１時間780mg
(4) トリエチルアミンボラン油状〔IR（cm-1）：
3200〜2900、2410〜2300、1480〜1460、
1180〕、１時間、760mg(1) t-Butylamine borane mp92-94℃ (decomposition), 10 minutes, 490 mg (2) Diethylamine borane oil [IR (cm -1 ):
3225, 3000-2900, 2410-2290, 1180], 10 minutes, 570 mg (3) Morpholine borane mp95-96℃, 780 mg for 1 hour (4) Triethylamine borane oil [IR (cm -1 ):
3200~2900, 2410~2300, 1480~1460,
1180], 1 hour, 760mg
Claims (1)
メチルホルムアミド中で反応させることを特徴と
するアミンボランの製造方法。1. A method for producing amine borane, which comprises reacting amine salts and sodium borohydride in dimethylformamide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8086779A JPS565490A (en) | 1979-06-27 | 1979-06-27 | Preparation of amine-borane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8086779A JPS565490A (en) | 1979-06-27 | 1979-06-27 | Preparation of amine-borane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS565490A JPS565490A (en) | 1981-01-20 |
| JPS6145996B2 true JPS6145996B2 (en) | 1986-10-11 |
Family
ID=13730286
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8086779A Granted JPS565490A (en) | 1979-06-27 | 1979-06-27 | Preparation of amine-borane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS565490A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63318983A (en) * | 1987-06-23 | 1988-12-27 | 株式会社タカラ | Deformable toy |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100449579B1 (en) * | 2002-02-06 | 2004-09-18 | 한국이엔에쓰 주식회사 | Process for Producting Morpholine-Borane |
-
1979
- 1979-06-27 JP JP8086779A patent/JPS565490A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63318983A (en) * | 1987-06-23 | 1988-12-27 | 株式会社タカラ | Deformable toy |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS565490A (en) | 1981-01-20 |
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