JPH06340675A - Production of perfluoroalkyltrimethylsilane - Google Patents
Production of perfluoroalkyltrimethylsilaneInfo
- Publication number
- JPH06340675A JPH06340675A JP3206972A JP20697291A JPH06340675A JP H06340675 A JPH06340675 A JP H06340675A JP 3206972 A JP3206972 A JP 3206972A JP 20697291 A JP20697291 A JP 20697291A JP H06340675 A JPH06340675 A JP H06340675A
- Authority
- JP
- Japan
- Prior art keywords
- perfluoroalkyltrimethylsilane
- solvent
- acetonitrile
- producing
- reaction
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 42
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052740 iodine Chemical group 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000001577 simple distillation Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000005406 washing Methods 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052794 bromium Inorganic materials 0.000 abstract description 3
- 239000011630 iodine Chemical group 0.000 abstract description 2
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 9
- 238000004821 distillation Methods 0.000 description 7
- FDIOSTIIZGWENY-UHFFFAOYSA-N n-[bis(diethylamino)phosphanyl]-n-ethylethanamine Chemical compound CCN(CC)P(N(CC)CC)N(CC)CC FDIOSTIIZGWENY-UHFFFAOYSA-N 0.000 description 7
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000004820 halides Chemical class 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- -1 ketone compound Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RJCQBQGAPKAMLL-UHFFFAOYSA-N bromotrifluoromethane Chemical compound FC(F)(F)Br RJCQBQGAPKAMLL-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
- MWKJTNBSKNUMFN-UHFFFAOYSA-N trifluoromethyltrimethylsilane Chemical compound C[Si](C)(C)C(F)(F)F MWKJTNBSKNUMFN-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- USYVEDJTMCGMKN-UHFFFAOYSA-N 1-bromo-1,1,2,2,2-pentafluoroethane Chemical compound FC(F)(F)C(F)(F)Br USYVEDJTMCGMKN-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- BAYGVMXZJBFEMB-UHFFFAOYSA-N 4-(trifluoromethyl)phenol Chemical compound OC1=CC=C(C(F)(F)F)C=C1 BAYGVMXZJBFEMB-UHFFFAOYSA-N 0.000 description 1
- 239000005514 Flazasulfuron Substances 0.000 description 1
- HWATZEJQIXKWQS-UHFFFAOYSA-N Flazasulfuron Chemical compound COC1=CC(OC)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CN=2)C(F)(F)F)=N1 HWATZEJQIXKWQS-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000011090 industrial biotechnology method and process Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- ZHSKFONQCREGOG-UHFFFAOYSA-N triethyl(trifluoromethyl)silane Chemical compound CC[Si](CC)(CC)C(F)(F)F ZHSKFONQCREGOG-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- VSQQQLOSPVPRAZ-RRKCRQDMSA-N trifluridine Chemical compound C1[C@H](O)[C@@H](CO)O[C@H]1N1C(=O)NC(=O)C(C(F)(F)F)=C1 VSQQQLOSPVPRAZ-RRKCRQDMSA-N 0.000 description 1
- 229960003962 trifluridine Drugs 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、パーフルオロアルキル
トリメチルシランの製造方法に関するものである。FIELD OF THE INVENTION The present invention relates to a method for producing perfluoroalkyltrimethylsilane.
【０００２】[0002]
【従来の技術】パーフルオロアルキルトリメチルシラン
は、化学的又は生理的性質等の面で重要な含フッ素化合
物の合成原料として、特にパーフルオロアルキル化剤と
して有用な化合物である。例えば、「ジャーナル オブ
オーガニックケミストリー」（Ｊｏｕｒｎａｌ ｏｆ
Ｏｒｇａｎｉｃ Ｃｈｅｍｉｓｔｒｙ）５６，９８４
（１９９１）に記載のごとき、アルデヒド、ケトン化合
物をテトラブチルアンモニウムフルオライドの存在下パ
ーフルオロアルキルトリメチルシランと反応することに
より、α−パーフルオロアルキルアルコールが得られ
る。又、「ジャーナル オブ オーガニックケミストリ
ー」（Ｊｏｕｒｎａｌ ｏｆ Ｏｒｇａｎｉｃ Ｃｈｅ
ｍｉｓｔｒｙ）５４，２８７３（１９８９）に記載のご
とき、ベンゾキノンを塩基の存在下トリフルオロメチル
トリエチルシランと反応させた後、還元によりｐ−トリ
フルオロメチルフェノールが得られる。このようなトリ
フルオロメチル基を有する化合物は、たとえば制癌剤と
して知られているトリフルオロチミジンや除草剤として
上市されているＦｌａｚａｓｕｌｆｕｒｏｎなどの医農
薬品の原料として、また透過性ポリイミドなどの高機能
性物質の材料などとして広く利用されている。2. Description of the Related Art Perfluoroalkyltrimethylsilane is a compound useful as a raw material for synthesizing a fluorine-containing compound which is important in terms of chemical or physiological properties, especially as a perfluoroalkylating agent. For example, “Journal of Organic Chemistry” (Journal of
Organic Chemistry) 56 , 984
As described in (1991), by reacting an aldehyde or ketone compound with perfluoroalkyltrimethylsilane in the presence of tetrabutylammonium fluoride, α-perfluoroalkyl alcohol can be obtained. In addition, "Journal of Organic Chemistry" (Journal of Organic Chem
mistry) 54 , 2873 (1989), benzoquinone is reacted with trifluoromethyltriethylsilane in the presence of a base and then reduced to give p-trifluoromethylphenol. Such a compound having a trifluoromethyl group can be used as a raw material for medical and agricultural chemicals such as trifluorothymidine known as an anti-cancer agent and Flazasulfuron marketed as a herbicide, and a highly functional substance such as a permeable polyimide. It is widely used as a material.
【０００３】パーフルオロアルキルトリメチルシランの
従来の合成法は、パーフルオロアルキルハライドとクロ
ロトリメチルシランをヘキサエチルホスフォラストリア
ミドの存在下反応させる方法が知られている。例えば
「テトラヘドロン レター」（Ｔｅｔｒａｈｅｄｒｏｎ
Ｌｅｔｔｅｒｓ）２５，２１９５（１９８４）あるい
は、「ジャーナル オブ オーガニックケミストリー」
（Ｊｏｕｒｎａｌ ｏｆＯｒｇａｎｉｃ Ｃｈｅｍｉｓ
ｔｒｙ）５６，９８４（１９９１）に記載のごとき、ベ
ンゾニトリルを溶媒とする方法、Ｇｅｒ．Ｏｆｆｅｎ．
ＤＥ３８０５５３４に記載のごときブチロニトリルを溶
媒とする方法が知られている。As a conventional synthesis method of perfluoroalkyltrimethylsilane, a method of reacting a perfluoroalkyl halide and chlorotrimethylsilane in the presence of hexaethylphosphorus triamide is known. For example, "Tetrahedron Letter" (Tetrahedron
Letters) 25 , 2195 (1984) or "Journal of Organic Chemistry".
(Journal of Organic Chemis
try) 56 , 984 (1991), using benzonitrile as a solvent, Ger. Offen.
A method using butyronitrile as a solvent as described in DE 3805534 is known.
【０００４】しかしながら、これら製造方法には工業的
技術として満足のいくものとは言い難い。つまり、ベン
ゾニトリルを溶媒とした場合、反応が−４０℃と低温を
必要とするのに対しベンゾニトリルの凝固点が−１２．
７５℃と高いため反応液がスラリー状となり攪拌が困難
であり収率も６５〜７０％と低い。すなわち反応を円滑
に進行させることが困難である。更に、ブチロニトリル
（ＢＰ１１７．５℃）を溶媒とした場合入手がほとんど
不可能であり、工業的にブチロニトリルを溶媒として使
用することは実際には不可能である。たとえ試薬として
少量入手が出来たとしても溶媒の値段が高く、蒸留によ
り回収が必要なため沸点の近いシラン化合物の合成、た
とえばＣ3 Ｆ7 ＳｉＭｅ3 ：ＢＰ８７℃の合成には適さ
ない。However, it is difficult to say that these manufacturing methods are satisfactory as industrial techniques. That is, when benzonitrile is used as a solvent, the reaction requires a low temperature of -40 ° C, whereas the freezing point of benzonitrile is -12.
Since the temperature is as high as 75 ° C., the reaction liquid becomes a slurry and stirring is difficult, and the yield is low at 65 to 70%. That is, it is difficult to make the reaction proceed smoothly. Furthermore, it is almost impossible to obtain butyronitrile (BP117.5 ° C.) as a solvent, and it is practically impossible to industrially use butyronitrile as a solvent. Even if a small amount can be obtained as a reagent, the cost of the solvent is high and it is necessary to recover it by distillation, so that it is not suitable for the synthesis of a silane compound having a close boiling point, for example, C 3 F 7 SiMe 3 : BP87 ° C.
【０００５】従って、該方法において、容易に入手でき
かつ安価な溶媒を用い、高収率で簡単な方法により目的
とするパーフルオロアルキルトリメチルシランを合成す
ることができれば、工業的価値は大きい。Therefore, if the desired perfluoroalkyltrimethylsilane can be synthesized by a simple method in a high yield using a solvent which is easily available and inexpensive, the industrial value is great.
【０００６】[0006]
【発明が解決しようとする課題】本発明者らは、上記の
ごとき状況に鑑みパーフルオロ脂肪族ハロゲン化物にヘ
キサエチルホスフォラストリアミド存在下クロロトリメ
チルシランを反応させることによりパーフルオロアルキ
ルトリメチルシランを合成する反応について、様々な溶
媒を用いて反応した結果、アセトニトリルを溶媒とする
ことにより単蒸留と水洗を組み合わせるだけで純度の高
い目的とするパーフルオロアルキルトリメチルシランを
収率良く容易に取得することができ本発明に到った。In view of the above situation, the inventors of the present invention react perfluoroaliphatic halide with chlorotrimethylsilane in the presence of hexaethylphosphorus triamide to give perfluoroalkyltrimethylsilane. As a result of reaction using various solvents for the reaction to synthesize, it is possible to easily obtain the target perfluoroalkyltrimethylsilane with high purity in high yield simply by combining simple distillation and washing with water by using acetonitrile as the solvent. The present invention has been completed.
【０００７】[0007]
【課題を解決するための手段】すなわち、本発明は、一
般式ＲｆＸ（但、式中Ｒｆは炭素数１〜３のパーフルオ
ロ脂肪族基、Ｘは臭素、沃素原子のいずれかを示す。）
で表されるパーフルオロ脂肪族ハロゲン化物をヘキサア
ルキルホスフォラストリアミドの存在下、クロロトリメ
チルシランと反応し、一般式ＲｆＳｉＭｅ3 （但、Ｒｆ
は前記したものに同じ）で表されるパーフルオロアルキ
ルトリメチルシランを生成する方法において、アセトニ
トリルを溶媒とすることを特徴とするパーフルオロアル
キルトリメチルシランの製造方法に係わるものである。That is, the present invention provides a compound represented by the general formula RfX (wherein Rf represents a perfluoroaliphatic group having 1 to 3 carbon atoms, and X represents either a bromine atom or an iodine atom).
The perfluoroaliphatic halide represented by the following formula is reacted with chlorotrimethylsilane in the presence of hexaalkylphosphorus triamide to give RfSiMe 3 (provided that Rf
Are the same as those described above) in the method for producing perfluoroalkyltrimethylsilane, wherein acetonitrile is used as a solvent in the method for producing perfluoroalkyltrimethylsilane.
【０００８】本発明で用いられるパーフルオロ脂肪族ハ
ロゲン化物（ＲｆＸ）としては種々のものが用いられ
る。ただし、反応の収率を考えた場合ハロゲン原子
（Ｘ）は臭素あるいは沃素であることが望ましい。ま
た、原料の価格を考慮に入れるとハロゲン原子は、臭素
であることが推奨される。As the perfluoroaliphatic halide (RfX) used in the present invention, various ones are used. However, considering the reaction yield, the halogen atom (X) is preferably bromine or iodine. Also, considering the raw material price, it is recommended that the halogen atom is bromine.
【０００９】本発明の反応は、０℃以下で行うことが出
来るが、通常は−５０℃〜−３０℃で行なうことが望ま
しい。The reaction of the present invention can be carried out at 0 ° C or lower, but it is usually desirable to carry out at -50 ° C to -30 ° C.
【００１０】本発明の反応は、塩基としてヘキサエチル
ホスフォラストリアミドを用いるが、他のヘキサアルキ
ルホスフォラストリアミドを用いることもできる。In the reaction of the present invention, hexaethylphosphorus triamide is used as the base, but other hexaalkylphosphorus triamide can be used.
【００１１】反応は、クロロトリメチルシランと当量か
少過剰の上記したパーフルオロ脂肪族ハロゲン化物を、
本発明において重要であるアセトニトリルに溶解し、所
定の温度で当量のヘキサエチルホスフォラストリアミド
を滴下する。反応終了後、生成物を単蒸留で留出せし
め、流出部を水洗するだけで目的とするパーフルオロア
ルキルトリメチルシランを得ることができる。アセトニ
トリルは蒸留により洗浄水から回収することができる。The reaction is carried out by mixing chlorotrimethylsilane with an equivalent or a slight excess of the above-mentioned perfluoroaliphatic halide.
It is dissolved in acetonitrile, which is important in the present invention, and an equivalent amount of hexaethylphosphorus triamide is added dropwise at a predetermined temperature. After completion of the reaction, the product can be distilled off by simple distillation, and the outflow portion can be washed with water to obtain the desired perfluoroalkyltrimethylsilane. Acetonitrile can be recovered from the wash water by distillation.
【００１２】[0012]
【発明の効果】アセトニトリルを溶剤として、ほとんど
副生成物を生じることなく、パーフルオロハロゲン化物
をほぼ定量的に目的とするパーフルオロアルキルトリメ
チルシランに変換する事ができる。しかしながら、生成
物の単離に際し、従来法（Ｇｅｒ．Ｏｆｆｅｎ．ＤＥ３
８０５５３４）に従いアセトニトリルを溶剤として反応
し、蒸留で生成したパーフルオロアルキルトリメチルシ
ラン、たとえばトリフルオロメチルトリメチルシランと
アセトニトリルを分離することを試みたが、沸点が近い
ために分離不可能であった。そこで、生成物を単蒸留で
留出せしめ、同伴したアセトニトリルを水洗したとこ
ろ、ほとんど純粋なパーフルオロアルキルトリメチルシ
ランを得ることができた。その結果、従来法では、溶媒
と目的物を分離するために精密蒸留が必要であるが、こ
れを省くことができ、精製に要する時間ならびに手間を
削減することが出来た。又、溶媒であるアセトニトリル
は入手し易く、従来法のベンゾニトリルやブチロニトリ
ルに比べ非常に安価である。INDUSTRIAL APPLICABILITY Using acetonitrile as a solvent, a perfluorohalide can be almost quantitatively converted into a target perfluoroalkyltrimethylsilane with almost no by-products. However, in the isolation of the product, conventional methods (Ger. Offen. DE3
According to 805534), an attempt was made to react with acetonitrile as a solvent to separate perfluoroalkyltrimethylsilane produced by distillation, for example, trifluoromethyltrimethylsilane from acetonitrile, but it was impossible to separate because of the close boiling point. Therefore, when the product was distilled off by simple distillation and the entrained acetonitrile was washed with water, almost pure perfluoroalkyltrimethylsilane could be obtained. As a result, in the conventional method, precision distillation is required to separate the solvent from the target substance, but this can be omitted, and the time and labor required for purification can be reduced. Acetonitrile, which is a solvent, is easily available and is much cheaper than conventional benzonitrile and butyronitrile.
【００１３】以上本発明は、従来にない効率的でかつ簡
便なパーフルオロアルキルトリメチルシランの製造法を
提供するものである。As described above, the present invention provides an unprecedented efficient and simple method for producing perfluoroalkyltrimethylsilane.
【００１４】[0014]
【実施例】以下に実施例および比較例により本発明を更
に詳細に説明するが、本発明はこれらに限定されるもの
ではない。The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
【００１５】実施例１ コールドフィンガー、温度計、攪拌機、ガス導入管を取
り付けた３Ｌフラスコに、アセトニトリル１Ｌ，クロロ
トリメチルシラン３２０ｍＬを加え、−４０℃に冷却し
ながら、ブロモトリフルオロメタン３８０ｇを導入し
た。−４０℃でヘキサエチルホスフォラストリアミド６
２４ｇを１時間かけて敵下した後、冷却を止め徐々に室
温まで昇温して反応を終了した。単蒸留装置をフラスコ
に取り付け、生成物を蒸留したところ、アセトニトリル
を含む生成物が得られた。この粗生成物を飽和食塩水で
四回洗浄することにより、３２４．４ｇのトリフルオロ
メチルトリメチルシラン（ＣＦ3 ＳｉＭｅ3 ）を得ら
れ、ガスクロマト分析により９８．８％の純度であっ
た。Example 1 1 L of acetonitrile and 320 mL of chlorotrimethylsilane were added to a 3 L flask equipped with a cold finger, a thermometer, a stirrer and a gas introduction tube, and 380 g of bromotrifluoromethane was introduced while cooling to -40 ° C. Hexaethylphosphorus triamide 6 at -40 ° C
After 24 g was controlled over 1 hour, cooling was stopped and the temperature was gradually raised to room temperature to complete the reaction. When a simple distillation apparatus was attached to the flask and the product was distilled, a product containing acetonitrile was obtained. The crude product was washed with saturated saline four times to obtain 324.4 g of trifluoromethyltrimethylsilane (CF 3 SiMe 3 ), which was 98.8% pure by gas chromatography analysis.
【００１６】この結果、収率は９０％であった。また、
より純度の高いＣＦ3 ＳｉＭｅ3 は、モレキュラーシー
ブ４Ａ（商品名：和光純薬社製）で乾燥後、精密蒸留す
ることによって純度９９％以上のものが得られ、生成物
の沸点は５５℃であった。As a result, the yield was 90%. Also,
CF 3 SiMe 3 with higher purity is obtained by drying with molecular sieve 4A (trade name: manufactured by Wako Pure Chemical Industries, Ltd.) and then subjecting it to precision distillation to obtain a product having a purity of 99% or more, and the boiling point of the product is 55 ° C. there were.
【００１７】比較例１ クロロトリメチルシラン２５ｍＬ、ブロモトリフルオロ
メタン３６ｇ、ヘキサエチルホスフォラストリアミド５
０ｇを用いプロピオニトリル１００ｍＬ中で、他の条件
は実施例１と全く同じ条件で反応した。飽和食塩水によ
る洗浄により２２ｇのＣＦ3 ＳｉＭｅ3 が得られ、ガス
クロマト分析の結果、純度が９７％であった。また、収
率は７７％であった。Comparative Example 1 Chlorotrimethylsilane 25 mL, bromotrifluoromethane 36 g, hexaethylphosphorus triamide 5
The reaction was carried out under the same conditions as in Example 1 except that 0 g was used in 100 mL of propionitrile. 22 g of CF 3 SiMe 3 was obtained by washing with saturated saline, and the purity was 97% as a result of gas chromatography analysis. The yield was 77%.
【００１８】比較例２ 溶媒としてブチロニトリルを用いる以外、比較例１と全
く同じ条件で反応し、飽和食塩水による洗浄により２４
ｇのＣＦ3 ＳｉＭｅ3 が得られた。このＣＦ3ＳｉＭｅ3
は、洗浄を二十回行ったにもかかわらず、ガスクロマ
ト分析の結果、純度が９５％のものしか得られなかっ
た。又、収率は８４％であった。Comparative Example 2 The reaction was carried out under the same conditions as in Comparative Example 1 except that butyronitrile was used as the solvent, and the reaction was carried out with a saturated saline solution to give 24
g of CF 3 SiMe 3 was obtained. This CF 3 SiMe 3
As a result of the gas chromatographic analysis, only 95% of the purity was obtained even though the washing was performed 20 times. The yield was 84%.
【００１９】比較例３ 比較例２と全く同じ条件でブチロニトリルを溶媒として
反応し、生成物を単蒸留した後に精密蒸留により２２ｇ
のＣＦ3 ＳｉＭｅ3 が得られた。収率は７７％であっ
た。Comparative Example 3 Under the same conditions as in Comparative Example 2, butyronitrile was used as a solvent for reaction, the product was subjected to simple distillation, and then 22 g by precision distillation.
CF 3 SiMe 3 was obtained. The yield was 77%.
【００２０】実施例２ クロロトリメチルシラン６８ｍＬ、ブロモペンタフルオ
ロエタン１２８ｇ、ヘキサエチルホスフォラストリアミ
ド１３２ｇを用いアセトニトリル２２０ｍＬ中で、他の
条件は実施例１と全く同じ条件で反応した。飽和食塩水
による洗浄により９２．７ｇのペンタフルオロエチルト
リメチルシラン（Ｃ2 Ｆ5 ＳｉＭｅ3 ）が得られ、ガス
クロマト分析の結果、純度が９８．０％であった。Example 2 68 mL of chlorotrimethylsilane, 128 g of bromopentafluoroethane, and 132 g of hexaethylphosphorus triamide were used in 220 mL of acetonitrile, and other conditions were exactly the same as in Example 1. By washing with saturated saline, 92.7 g of pentafluoroethyltrimethylsilane (C 2 F 5 SiMe 3 ) was obtained, and the result of gas chromatography analysis showed that the purity was 98.0%.
【００２１】この結果、収率は９０％であった。より純
度の高いＣ2 Ｆ5 ＳｉＭｅ3 は、モレキュラーシーブ４
Ａ（前出）で乾燥後、精密蒸留することによって純度９
９％以上のものが得られ、生成物の沸点は６９℃であっ
た。As a result, the yield was 90%. The more pure C 2 F 5 SiMe 3 is a molecular sieve 4
After drying with A (previously mentioned), precision distillation yields a purity of 9
9% or more was obtained, and the boiling point of the product was 69 ° C.
Claims (1)
〜３のパーフルオロ脂肪族基、Ｘは臭素、沃素原子のい
ずれかを示す）で表されるフルオロ脂肪族ハロゲン化物
をヘキサアルキルホスフォラストリアミドの存在下、ク
ロロトリメチルシランと反応し、一般式ＲｆＳｉＭｅ3
（但、Ｒｆは前記したものに同じ）で表されるパーフル
オロアルキルトリメチルシランを生成する方法におい
て、アセトニトリルを溶媒とし、反応液を単蒸留した後
に、水洗いすることを特徴とするパーフルオロアルキル
トリメチルシランの製造方法。1. A general formula RfX (wherein Rf is 1 carbon atom)
A perfluoroaliphatic group of 3 to X, X represents either a bromine atom or an iodine atom), and is reacted with chlorotrimethylsilane in the presence of hexaalkylphosphorus triamide to give a compound represented by the general formula: RfSiMe 3
In the method for producing perfluoroalkyltrimethylsilane represented by (wherein Rf is the same as above), acetonitrile is used as a solvent, the reaction solution is subjected to simple distillation, and then washed with water. Method for producing silane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20697291A JP3200099B2 (en) | 1991-08-19 | 1991-08-19 | Method for producing perfluoroalkyltrimethylsilane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20697291A JP3200099B2 (en) | 1991-08-19 | 1991-08-19 | Method for producing perfluoroalkyltrimethylsilane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06340675A true JPH06340675A (en) | 1994-12-13 |
| JP3200099B2 JP3200099B2 (en) | 2001-08-20 |
Family
ID=16532054
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20697291A Expired - Fee Related JP3200099B2 (en) | 1991-08-19 | 1991-08-19 | Method for producing perfluoroalkyltrimethylsilane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3200099B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005511665A (en) * | 2001-11-29 | 2005-04-28 | ユニバーシティ・オブ・サザン・カリフォルニア | Preparation of fluorinated alkylsilanes mediated by magnesium |
| KR100673554B1 (en) * | 2005-10-24 | 2007-01-24 | 한국과학기술연구원 | Method for preparing of trifluoromethyltrialkylsilane |
| CN107880069A (en) * | 2017-11-28 | 2018-04-06 | 湖南有色郴州氟化学有限公司 | A kind of trifluoromethyl（Trimethyl）The preparation method of silane |
| JP2019172636A (en) * | 2018-03-29 | 2019-10-10 | 国立研究開発法人産業技術総合研究所 | Method for producing organosilicon compound using halosilane as raw material |
| CN113105492A (en) * | 2021-04-15 | 2021-07-13 | 上海立科化学科技有限公司 | Preparation method of trifluoromethyl trimethylsilane |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6083006B1 (en) * | 2016-02-17 | 2017-02-22 | 株式会社シーティーアイ | Container manufacturing method and laser processing system |
-
1991
- 1991-08-19 JP JP20697291A patent/JP3200099B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005511665A (en) * | 2001-11-29 | 2005-04-28 | ユニバーシティ・オブ・サザン・カリフォルニア | Preparation of fluorinated alkylsilanes mediated by magnesium |
| KR100673554B1 (en) * | 2005-10-24 | 2007-01-24 | 한국과학기술연구원 | Method for preparing of trifluoromethyltrialkylsilane |
| CN107880069A (en) * | 2017-11-28 | 2018-04-06 | 湖南有色郴州氟化学有限公司 | A kind of trifluoromethyl（Trimethyl）The preparation method of silane |
| CN107880069B (en) * | 2017-11-28 | 2021-02-19 | 湖南有色郴州氟化学有限公司 | Preparation method of trifluoromethyl (trimethyl) silane |
| JP2019172636A (en) * | 2018-03-29 | 2019-10-10 | 国立研究開発法人産業技術総合研究所 | Method for producing organosilicon compound using halosilane as raw material |
| CN113105492A (en) * | 2021-04-15 | 2021-07-13 | 上海立科化学科技有限公司 | Preparation method of trifluoromethyl trimethylsilane |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3200099B2 (en) | 2001-08-20 |
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