KR101249361B1 - Manufacturing process of high-purity Tris(trialkylsilyl)Phosphite - Google Patents

Manufacturing process of high-purity Tris(trialkylsilyl)Phosphite Download PDF

Info

Publication number
KR101249361B1
KR101249361B1 KR1020100128770A KR20100128770A KR101249361B1 KR 101249361 B1 KR101249361 B1 KR 101249361B1 KR 1020100128770 A KR1020100128770 A KR 1020100128770A KR 20100128770 A KR20100128770 A KR 20100128770A KR 101249361 B1 KR101249361 B1 KR 101249361B1
Authority
KR
South Korea
Prior art keywords
phosphite
trialkylsilyl
tris
solvent
catalyst
Prior art date
Application number
KR1020100128770A
Other languages
Korean (ko)
Other versions
KR20120067398A (en
Inventor
이남석
권영길
황의형
이정규
전어진
Original Assignee
리켐주식회사
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 리켐주식회사 filed Critical 리켐주식회사
Priority to KR1020100128770A priority Critical patent/KR101249361B1/en
Publication of KR20120067398A publication Critical patent/KR20120067398A/en
Application granted granted Critical
Publication of KR101249361B1 publication Critical patent/KR101249361B1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00583—Features relative to the processes being carried out
    • B01J2219/0059—Sequential processes

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)

Abstract

본 발명은 별도의 촉매 및 용매 없이 트리스(트리알킬실릴)포스파이트를 제조하는 방법에 관한 것으로, 상세하게는 아인산 및 헥사알킬디실라잔 유도체를 반응시킨 다음, 연속적으로 나트륨 금속을 첨가하여 고순도 트리스(트리알킬실릴)포스파이트를 제조하는 방법에 관한 것이다.
촉매 및 용매없이 이용한 본 발명은 짧은 시간내에 합성하고, 나트륨 금속을 이용하여 정제 없이 한번 반응으로 고순도 화합물을 합성할 수 있다. 또한, 기존에 사용하는 촉매 및 용매 사용이 없기에 산업 공정상 용이하다는 장점을 가지고 있다. 따라서 화학 공업 분야에서 유용하게 활용될 수 있다.The present invention relates to a process for preparing tris (trialkylsilyl) phosphite without a separate catalyst and solvent, specifically, high purity tris by reacting phosphorous acid and hexaalkyldisilazane derivatives, followed by the addition of sodium metal in succession. A method for producing (trialkylsilyl) phosphite.
The present invention used without a catalyst and a solvent can be synthesized in a short time and a high purity compound can be synthesized in a single reaction without purification using sodium metal. In addition, there is an advantage in the industrial process because there is no use of the catalyst and solvent used in the past. Therefore, it can be usefully used in the chemical industry.

Description

고순도 트리스(트리알킬실릴)포스파이트의 제조 방법{Manufacturing process of high-purity Tris(trialkylsilyl)Phosphite}Manufacturing process of high-purity Tris (trialkylsilyl) Phosphite}

본 발명은 별도의 촉매 및 용매 없이 트리스(트리알킬실릴)포스파이트를 제조하는 방법에 관한 것으로, 상세하게는 아인산 및 헥사알킬디실라잔 유도체를 반응시킨 다음, 연속적으로 나트륨 금속을 첨가하여 고순도 트리스(트리알킬실릴)포스파이트를 제조하는 방법에 관한 것이다. The present invention relates to a process for preparing tris (trialkylsilyl) phosphite without a separate catalyst and solvent, specifically, high purity tris by reacting phosphorous acid and hexaalkyldisilazane derivatives, followed by the addition of sodium metal in succession. A method for producing (trialkylsilyl) phosphite.

알코올에 실릴화시키는 반응은 많이 알려져 있다. 일반적으로 알려진 방법의 예로는 PBr3/ZnCl2/에틸 트리메틸실릴 에테르 (Zh . Obshchh . Khim ., 1965, 35, 106), (Chem . Abstr ., 1965, 62, 13173), H3PO3/TMSCl/TEA/THF/Ether (J. Org . Chem. 1981, 46, 2097), H3PO3/TMSCl/TEA/THF/Ether (Can . J. Chem ., 1979, 57, 236) 및 H3PO3/TMSCl/TEA/THF/Na (Chem . Rev ., 1961, 61, 31) 등을 사용하는 방법을 들 수 있다.Many reactions to silylate alcohols are known. Examples of methods generally known in the PBr 3 / ZnCl 2 / ethyl trimethylsilyl ether (Zh. Obshchh. Khim., 1965, 35, 106), (Chem. Abstr., 1965, 62, 13173), H 3 PO 3 / TMSCl / TEA / THF / Ether ( J. Org . Chem. 1981, 46 , 2097), H 3 PO 3 / TMSCl / TEA / THF / Ether ( Can . J. Chem . , 1979, 57 , 236) and H 3 PO 3 / TMSCl / TEA / THF / Na a method using a (Chem. Rev., 1961, 61, 31) or the like.

그러나, 상기 방법들은 다양한 용매 및 촉매를 사용하여 반응을 진행하는 반응조건 등을 요구하고 있다. 또한 상기 방법들에서는 반응을 진행 후, 여과하는 과정과 용매를 제거하여 다음 과정을 진행하는 단점을 가지고 있기 때문에 반응 후 과정이 복잡하고, 비용적인 측면에서 효율적이지 못하다.However, the above methods require reaction conditions for carrying out the reaction using various solvents and catalysts. In addition, in the above methods, after the reaction, the process of filtration and the removal of the solvent have the disadvantage of proceeding to the next process, so the post-reaction process is complicated and inefficient in terms of cost.

예를 들면, 아래의 반응식 A와 같이 용매를 사용하여 아인산에 실릴화 반응을 진행하는데 H3PO3/TMSCl/TEA/THF/Ether (J. Org . Chem . 1981, 46, 2097)을 사용하면, 트리에틸아민염의 생성으로 인해 테트라하이드로퓨란과 벤젠 및 에테르 등의 다양한 용매를 사용되게 된다. 반응 기체 부산물 또한 취급이 용이하지 못하며, 반응 완료하여 여과 및 추출하는 등 과정이 복잡해진다.For example, the reaction of phosphorylation in phosphorous acid using a solvent, as shown in Scheme A below, using H 3 PO 3 / TMSCl / TEA / THF / Ether ( J. Org . Chem . 1981, 46 , 2097) The production of triethylamine salts leads to the use of various solvents such as tetrahydrofuran, benzene and ether. Reaction gas by-products are also difficult to handle, and the process is complicated by completion of the reaction, filtration and extraction.

[반응식 A][Reaction Scheme A]

Figure 112010082871416-pat00001
Figure 112010082871416-pat00001

본 발명자들은 한단계 반응으로 고순도 트리스(트리메틸실릴)포스파이트 및 트리스(트리에틸실릴)포스파이트 합성 방법을 예의 연구해온 결과, 촉매 및 용매 없이도 이를 성취할 수 있다는 것을 발견하였다. 즉, 포스파이트 합성의 경우 관능기의 치환과 이동에 촉매나 용매없이도 합성 및 나트륨 금속을 이용하여 고순도 화합물을 합성할 수 있음을 발견하고 본 발명을 완성하였다.The inventors have intensively studied the methods of synthesizing high purity tris (trimethylsilyl) phosphite and tris (triethylsilyl) phosphite in one step reaction and found that this can be achieved without catalyst and solvent. That is, in the case of phosphite synthesis, the present inventors have found that high purity compounds can be synthesized by using sodium metal and synthesis without the use of catalysts or solvents for the substitution and transfer of functional groups.

따라서 본 발명은 촉매 및 용매 없이 아인산과 헥사알킬디실라잔 및나트륨 금속을 이용하여 고순도 트리스(트리알킬실릴)포스파이트를 제조하는 방법을 제공한다.The present invention thus provides a process for the preparation of high purity tris (trialkylsilyl) phosphites using phosphorous acid, hexaalkyldisilazane and sodium metal without catalyst and solvent.

본 발명의 또 다른 목적은 용매 사용이 없기에 한단계 반응의 실릴화 반응 방법을 제공하는 것이다.Another object of the present invention is to provide a method for silylation of a one-step reaction because there is no solvent.

본 발명은 별도의 촉매 및 용매 없이 트리스(트리알킬실릴)포스파이트를 제조하는 방법에 관한 것으로, 상세하게는 아인산 및 하기 화학식 2의 헥사알킬디실라잔 유도체를 반응시킨 다음, 연속적으로 나트륨 금속을 첨가하여 하기 화학식 1의 고순도 트리스(트리알킬실릴)포스파이트를 제조하는 방법에 관한 것이다.The present invention relates to a process for preparing tris (trialkylsilyl) phosphite without a separate catalyst and solvent, and in particular, by reacting phosphorous acid and a hexaalkyldisilazane derivative of the following formula (2), and subsequently sodium metal It relates to a method for producing a high purity tris (trialkylsilyl) phosphite of the following general formula (1).

[화학식 1][Formula 1]

Figure 112010082871416-pat00002
Figure 112010082871416-pat00002

[화학식 2][Formula 2]

Figure 112010082871416-pat00003
Figure 112010082871416-pat00003

[상기 화학식 1 및 2에서, R은 메틸 또는 에틸이다.]
[In Formulas 1 and 2, R is methyl or ethyl.]

본 발명에서 사용되는 헥사알킬디실라잔은 헥사메틸디실라잔(HMDS) 또는 헥사에틸디실라잔(HEDS)로, 아인산 1 당량에 대하여 1 내지 3당량, 바람직하게는 1.5 내지 2당량의 범위 내에서 사용된다. 상기 헥사알킬디실라잔의 사용량이 1당량 미만이면 미 반응 인산이 다량으로 존재하여서 수율저하의 요인이 될 수 있고, 3당량 초과하여도 역시 HMDS 또는 HEDS가 남게 되어 정제시 순도가 저하되는 문제점이 발생한다.The hexaalkyldisilazane used in the present invention is hexamethyldisilazane (HMDS) or hexaethyldisilazane (HEDS), which is 1 to 3 equivalents, preferably 1.5 to 2 equivalents based on 1 equivalent of phosphorous acid. Used in If the amount of the hexaalkyldisilazane used is less than 1 equivalent, unreacted phosphoric acid may be present in a large amount, which may cause a decrease in yield, and even after 3 equivalents, HMDS or HEDS remains, resulting in a decrease in purity during purification. Occurs.

상기 반응은 촉매 및 용매의 첨가 없이 반응이 진행된다. 특별히 첨가되는 촉매나 용매는 제한되지 아니하고 과량 첨가할 수 있으나, 촉매 및 용매의 첨가 없이 반응을 진행하는 것이 바람직하다.The reaction proceeds without addition of catalyst and solvent. The catalyst or solvent to be added is not particularly limited and may be added in excess, but it is preferable to proceed with the reaction without addition of the catalyst and the solvent.

상기 반응은 100 내지 160℃에서 실시되며, 더욱 구제적으로 아인산 및 헥사알킬디실라잔 유도체의 반응은 100 내지 150℃, 바람직하게는 120 내지 130℃에서 수행하며, 나트륨 금속을 첨가하는 반응은 130 내지 160℃, 바람직하게는 140 내지 150℃에서 수행하고, 상기 반응들은 다른 관능기에 영향이 없을 경우 반응액을 환류시켜 반응을 수행할 수 있다.
The reaction is carried out at 100 to 160 ° C, more specifically the reaction of the phosphorous acid and hexaalkyldisilazane derivatives is carried out at 100 to 150 ° C, preferably 120 to 130 ° C, the reaction of adding sodium metal is 130 To 160 ° C, preferably 140 to 150 ° C, and the reactions may be carried out by refluxing the reaction solution when no other functional group is affected.

본 발명에 따른 상기 화학식 1의 트리스(트리알킬실릴)포스파이트를 제조하는 방법을 반응식으로 도시하면 하기와 같다.A method of preparing tris (trialkylsilyl) phosphite of Chemical Formula 1 according to the present invention is shown in the following scheme.

[반응식 1][Reaction Scheme 1]

Figure 112010082871416-pat00004
Figure 112010082871416-pat00004

[상기 R은 메틸 또는 에틸이다.][Wherein R is methyl or ethyl]

본 발명에 따른 트리스(트리알킬실릴)포스파이트의 제조방법은 별도의 촉매 및 용매 없이 아인산과 헥사메틸디실라잔 또는 헥사에틸디실라잔을 이용하여 여과 및 정제의 과정없이 바로 혼합물에 나트륨 금속을 첨가하여 고순도 트리스(트리메틸실릴)포스파이트 및 트리스(트리에틸실릴)포스파이트를 제조할 수 있는 장점이 있다. 또한, 기존에 사용되는 방법들에 필수성분으로 사용된 촉매 및 용매 사용이 없어 산업 공정상 용이하다는 장점을 가지고 있다. 따라서 화학 공업 분야에서 유용하게 활용될 수 있다.In the process for preparing tris (trialkylsilyl) phosphite according to the present invention, using a phosphorous acid and hexamethyldisilazane or hexaethyldisilazane without a separate catalyst and solvent, sodium metal is added directly to the mixture without filtration and purification. There is an advantage in that high purity tris (trimethylsilyl) phosphite and tris (triethylsilyl) phosphite can be prepared by addition. In addition, there is no catalyst and solvent used as essential components in the existing methods have the advantage of easy industrial process. Therefore, it can be usefully used in the chemical industry.

이하, 아래의 실시예를 들어 본 발명을 보다 상세히 설명할 것이나, 본 발명의 범위가 이들 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to these examples.

[실시예 1] 트리스(트리메틸실릴)포스파이트의 제조 Example 1 Preparation of Tris (trimethylsilyl) phosphite

아인산 3,000 g(35.84 mol)을 반응기에 넣고, 교반하면서 헥사메틸디실라잔 11.65 l(53.78 mol)을 천천히 5시간동안 적가하였다. 적가 완료 후, 125 ℃에서 3시간동안 가열환류하였다. 나트륨 금속 245 g(10.76 mol)을 천천히 적가 후, 145 ℃에서 10시간동안 가열환류하였다. 반응이 완료된 후, 실온으로 냉각하고, 분별 증류로 목적 생성물인 트리스(트리메틸실릴)포스파이트 7,813 g(수율 73%)을 얻었다.3,000 g (35.84 mol) of phosphorous acid were placed in a reactor, and 11.65 l (53.78 mol) of hexamethyldisilazane was slowly added dropwise for 5 hours while stirring. After the addition was completed, the mixture was heated to reflux at 125 ° C. for 3 hours. 245 g (10.76 mol) of sodium metal was slowly added dropwise and then heated to reflux at 145 ° C. for 10 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and fractional distillation gave 7,813 g (yield 73%) of tris (trimethylsilyl) phosphite as a desired product.

1H-NMR 300MHz(C6H6) δ ; 0.2 (s, 27H, -Si( CH 3 )3)
 1 H-NMR 300 MHz (C 6 H 6 ) δ; 0.2 (s, 27H, -Si ( CH 3 ) 3 )

[실시예 2] 트리스(트리에틸실릴)포스파이트의 제조 Example 2 Preparation of Tris (triethylsilyl) phosphite

아인산 956 mg(11.67 mmol)을 반응기에 넣고, 교반하면서 헥사에틸디실라잔 5 g(17.50 mmol)을 천천히 5시간동안 적가하였다. 적가 완료 후, 125 ℃에서 3시간동안 가열환류하였다. 나트륨 금속 80.5 mg(3.50 mmol)을 천천히 적가 후, 145 ℃에서 10시간동안 가열환류하였다. 반응이 완료된 후, 실온으로 냉각하고, 분별 증류로 목적 생성물인 트리스(트리에틸실릴)포스파이트 3.3 g(수율 68%)을 얻었다.956 mg (11.67 mmol) of phosphorous acid were placed in a reactor, and 5 g (17.50 mmol) of hexaethyldisilazane was slowly added dropwise for 5 hours while stirring. After the addition was completed, the mixture was heated to reflux at 125 ° C. for 3 hours. 80.5 mg (3.50 mmol) of sodium metal was slowly added dropwise and then heated to reflux at 145 ° C. for 10 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and fractional distillation gave 3.3 g (yield 68%) of tris (triethylsilyl) phosphite as a target product.

1H-NMR 300MHz(C6H6) δ ; 0.89 (m, 27H, -Si(CH2 CH 3 )3), 1.05 (m, 18H, -Si( CH 2 CH3)3) 1 H-NMR 300 MHz (C 6 H 6 ) δ; 0.89 (m, 27H, -Si (CH 2 CH 3 ) 3 ), 1.05 (m, 18H, -Si ( CH 2 CH 3 ) 3 )

Claims (4)

별도의 촉매 및 용매 없이 100 내지 160℃에서 아인산 및 하기 화학식 2의 헥사알킬디실라잔 유도체를 반응시킨 다음, 연속적으로 나트륨 금속을 첨가하여 하기 화학식 1의 트리스(트리알킬실릴)포스파이트를 제조하는 방법.
[화학식 1]
Figure 112012081216072-pat00005

[화학식 2]
Figure 112012081216072-pat00006

[상기 화학식 1 및 2에서, R은 메틸 또는 에틸이다.]To react the phosphorous acid and the hexaalkyldisilazane derivative of the formula (2) at 100 to 160 ℃ without a separate catalyst and solvent, and subsequently adding sodium metal to prepare a tris (trialkylsilyl) phosphite of the formula Way.
[Formula 1]
Figure 112012081216072-pat00005

(2)
Figure 112012081216072-pat00006

[In Formulas 1 and 2, R is methyl or ethyl.] 제 1항에 있어서,
상기 화학식 2의 헥사알킬디실라잔 유도체의 사용량은 아인산 1당량에 대하여 1 내지 3 당량인 방법.The method of claim 1,
The amount of the hexaalkyldisilazane derivative of Formula 2 is 1 to 3 equivalents based on 1 equivalent of phosphorous acid. 제 1항에 있어서,
상기 나트륨 금속의 사용량은 아인산 1당량에 대하여 0.2 내지 0.5 당량인 방법.The method of claim 1,
The sodium metal is used in an amount of 0.2 to 0.5 equivalents based on 1 equivalent of phosphorous acid. 삭제delete
KR1020100128770A 2010-12-16 2010-12-16 Manufacturing process of high-purity Tris(trialkylsilyl)Phosphite KR101249361B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020100128770A KR101249361B1 (en) 2010-12-16 2010-12-16 Manufacturing process of high-purity Tris(trialkylsilyl)Phosphite

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020100128770A KR101249361B1 (en) 2010-12-16 2010-12-16 Manufacturing process of high-purity Tris(trialkylsilyl)Phosphite

Publications (2)

Publication Number Publication Date
KR20120067398A KR20120067398A (en) 2012-06-26
KR101249361B1 true KR101249361B1 (en) 2013-04-03

Family

ID=46686406

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020100128770A KR101249361B1 (en) 2010-12-16 2010-12-16 Manufacturing process of high-purity Tris(trialkylsilyl)Phosphite

Country Status (1)

Country Link
KR (1) KR101249361B1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110551151A (en) * 2018-05-30 2019-12-10 微宏动力***（湖州）有限公司 preparation method of phosphate or phosphite ester, electrolyte and secondary battery

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109232641B (en) * 2018-10-30 2020-12-25 九江天赐高新材料有限公司 Preparation method of tri (trimethylsilyl) phosphite ester
CN111233918B (en) * 2018-11-29 2022-05-17 张家港市国泰华荣化工新材料有限公司 Synthesis method of tris (trimethylsilyl) phosphite ester
CN109456361B (en) * 2018-12-14 2021-08-24 苏州祺添新材料有限公司 Synthesis method of tri (trihydrocarbylsilyl) phosphite ester

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5041586A (en) * 1990-11-29 1991-08-20 Dow Corning Corporation Method of preparing a silyphosphate mixture, silyphosphate mixture and its use in stabilizing metal silanolates in siloxane polymers
US5420322A (en) * 1994-08-31 1995-05-30 Mine Safety Appliances Company Preparation of alkali-metal hexamethydisilazanes
KR20100090150A (en) * 2009-02-05 2010-08-13 리켐주식회사 Manufacturing process of high-purity tris(trimethylsilyl) phosphate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5041586A (en) * 1990-11-29 1991-08-20 Dow Corning Corporation Method of preparing a silyphosphate mixture, silyphosphate mixture and its use in stabilizing metal silanolates in siloxane polymers
US5420322A (en) * 1994-08-31 1995-05-30 Mine Safety Appliances Company Preparation of alkali-metal hexamethydisilazanes
KR20100090150A (en) * 2009-02-05 2010-08-13 리켐주식회사 Manufacturing process of high-purity tris(trimethylsilyl) phosphate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
논문;PLENUM PUBLISHING CORPORATION *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110551151A (en) * 2018-05-30 2019-12-10 微宏动力***（湖州）有限公司 preparation method of phosphate or phosphite ester, electrolyte and secondary battery

Also Published As

Publication number Publication date
KR20120067398A (en) 2012-06-26

Similar Documents

Publication Publication Date Title
JP6788253B2 (en) Method for producing alkenyl phosphorus compound
KR101249361B1 (en) Manufacturing process of high-purity Tris(trialkylsilyl)Phosphite
US20090253925A1 (en) Method for the continuous production of silicon compounds bearing amino groups
JP5529591B2 (en) Method for preparing metal complexes of multidentate β-ketoiminate
JP6707668B2 (en) Cationic silicon (II) compound and method for producing the same
JP2004529863A (en) Method for producing β-phosphorated nitroxide radical
Schull et al. Synthesis of symmetrical triarylphosphines from aryl fluorides and red phosphorus: scope and limitations
JP5848201B2 (en) Method for producing aryldichlorophosphine
JP2008512451A (en) Method for producing alkyl phosphinate
EP1810975B1 (en) Method for producing phosphonates having an alcoholic hydroxy group
JP2002121165A (en) Method for producing unsaturated ketone
KR101195631B1 (en) New Synthetic Method of 9-[2-phosphonomethoxyethyl]adenine
JPH03397B2 (en)
JP4807549B2 (en) Siloxanes, silanols and silanes, and methods for producing the same
JP5926797B2 (en) Method for preparing bis (perfluoroalkyl) phosphinic anhydride
JP4526275B2 (en) Method for producing tetra-substituted phosphonium tetrakisaroyloxyborate and its precursor
WO2024015263A1 (en) Process for preparing phosphonate esters
JP4257414B2 (en) Release method of phosphine
JP4891536B2 (en) Method for producing aminoaryl group-containing organosilicon compound, and method for producing an intermediate thereof
JP6418679B2 (en) Method for producing heteroaryl compound
JP6262079B2 (en) 4- (2,2,2-trifluoroethoxy) -5- (trifluoromethyl) pyrimidine derivative and method for producing the same
JP4625741B2 (en) Method for producing secondary phosphine-borane complex
RU2400487C1 (en) Method for synthesis of n,n-dialkylamidofluoroanhydrides of alkyl(aryl)phosphonous acids
JP3430928B2 (en) Organoxydichlorophosphine
JP5258370B2 (en) Industrial production method of risedronic acid

Legal Events

Date Code Title Description
A201 Request for examination
E902 Notification of reason for refusal
E701 Decision to grant or registration of patent right
GRNT Written decision to grant
FPAY Annual fee payment

Payment date: 20160325

Year of fee payment: 4

FPAY Annual fee payment

Payment date: 20180309

Year of fee payment: 6

FPAY Annual fee payment

Payment date: 20190320

Year of fee payment: 7