JPH0312076B2 - - Google Patents
Info
- Publication number
- JPH0312076B2 JPH0312076B2 JP8344087A JP8344087A JPH0312076B2 JP H0312076 B2 JPH0312076 B2 JP H0312076B2 JP 8344087 A JP8344087 A JP 8344087A JP 8344087 A JP8344087 A JP 8344087A JP H0312076 B2 JPH0312076 B2 JP H0312076B2
- Authority
- JP
- Japan
- Prior art keywords
- silicon
- isocyanate
- carbamate
- ester
- 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.)
- Expired
Links
- 229910052710 silicon Inorganic materials 0.000 claims description 36
- 239000010703 silicon Substances 0.000 claims description 36
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 33
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 150000003973 alkyl amines Chemical class 0.000 claims description 9
- AKZWRTCWNXHHFR-PDIZUQLASA-N [(3S)-oxolan-3-yl] N-[(2S,3S)-4-[(5S)-5-benzyl-3-[(2R)-2-carbamoyloxy-2,3-dihydro-1H-inden-1-yl]-4-oxo-3H-pyrrol-5-yl]-3-hydroxy-1-phenylbutan-2-yl]carbamate Chemical compound NC(=O)O[C@@H]1Cc2ccccc2C1C1C=N[C@](C[C@H](O)[C@H](Cc2ccccc2)NC(=O)O[C@H]2CCOC2)(Cc2ccccc2)C1=O AKZWRTCWNXHHFR-PDIZUQLASA-N 0.000 claims description 5
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 5
- FZFAMSAMCHXGEF-UHFFFAOYSA-N chloro formate Chemical compound ClOC=O FZFAMSAMCHXGEF-UHFFFAOYSA-N 0.000 claims 2
- 150000003512 tertiary amines Chemical class 0.000 claims 2
- 150000001412 amines Chemical class 0.000 claims 1
- -1 isocyanate ester Chemical class 0.000 description 23
- 239000012948 isocyanate Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 11
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 9
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 6
- XOEUHCONYHZURQ-HNUBZJOYSA-N flurithromycin Chemical compound O([C@@H]1[C@@H](C)C(=O)O[C@@H]([C@@]([C@H](O)[C@@H](C)C(=O)[C@@](C)(F)C[C@@](C)(O)[C@H](O[C@H]2[C@@H]([C@H](C[C@@H](C)O2)N(C)C)O)[C@H]1C)(C)O)CC)[C@H]1C[C@@](C)(OC)[C@@H](O)[C@H](C)O1 XOEUHCONYHZURQ-HNUBZJOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- GTCAXTIRRLKXRU-UHFFFAOYSA-N methyl carbamate Chemical compound COC(N)=O GTCAXTIRRLKXRU-UHFFFAOYSA-N 0.000 description 3
- 150000003376 silicon Chemical class 0.000 description 3
- 239000005051 trimethylchlorosilane Substances 0.000 description 3
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- HXBPYFMVGFDZFT-UHFFFAOYSA-N allyl isocyanate Chemical compound C=CCN=C=O HXBPYFMVGFDZFT-UHFFFAOYSA-N 0.000 description 2
- GJEMZHNSJOJQPY-UHFFFAOYSA-N diethoxymethyl(3-isocyanatopropyl)silane Chemical compound CCOC(OCC)[SiH2]CCCN=C=O GJEMZHNSJOJQPY-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- AHWALFGBDFAJAI-UHFFFAOYSA-N phenyl carbonochloridate Chemical compound ClC(=O)OC1=CC=CC=C1 AHWALFGBDFAJAI-UHFFFAOYSA-N 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 229940082584 3-(triethoxysilyl)propylamine Drugs 0.000 description 1
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 1
- BIGOJJYDFLNSGB-UHFFFAOYSA-N 3-isocyanopropyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)CCC[N+]#[C-] BIGOJJYDFLNSGB-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- AOGYCOYQMAVAFD-UHFFFAOYSA-N chlorocarbonic acid Chemical class OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- UVVUGWBBCDFNSD-UHFFFAOYSA-N tetraisocyanatosilane Chemical class O=C=N[Si](N=C=O)(N=C=O)N=C=O UVVUGWBBCDFNSD-UHFFFAOYSA-N 0.000 description 1
- OJAJJFGMKAZGRZ-UHFFFAOYSA-N trimethyl(phenoxy)silane Chemical compound C[Si](C)(C)OC1=CC=CC=C1 OJAJJFGMKAZGRZ-UHFFFAOYSA-N 0.000 description 1
Description
産業上の利用分野
本発明はアルコキシシリル基を官能基として分
子内に有する含ケイ素イソシアン酸エステルの製
造方法に関し、更に詳述すれば、ハロゲノ蟻酸エ
ステルと含ケイ素アルキルアミンとから含ケイ素
カルバミン酸エステルを得ると共に、含ケイ素カ
ルバミン酸エステルを加熱して含ケイ素イソシア
ン酸エステルを製造する際に、同時に生成するア
ルコール類をトリアルキルシリル化し、含ケイ素
カルバミン酸エステルへの逆反応を抑えるように
した含ケイ素イソシアン酸エステルを有利に製造
する方法に関する。
従来の技術及び発明が解決しようとする問題点
含ケイ素イソシアン酸エステルはポリマー改質
材料として有用であると共に、ポリマー中にアル
コキシ基を容易に導入することができる材料とし
て注目されている。
この含ケイ素イソシアン酸エステルを製造する
方法としては、従来、シラン化合物とイソシアン
酸アリルを三塩化ロジウムの存在下でヒドロシリ
ル化反応を行なつて製造する方法が知られている
（特公昭55−40592号）。しかし、この方法は出発
原料として非常に毒性の高いイソシアン酸アリル
を使用しており、取り扱いの面で安全性上の種々
の問題を有している。
また、別の製造法の例しては、含ケイ素アルキ
ルアミンを出発物質とし、カルバミン酸のハロシ
リル塩誘導体を製造し、これを分解して含ケイ素
イソシアン酸エステルを得る方法（特公昭57−
57020号）、及び含ケイ素アルキルアミンよりカル
バミン酸メチルエステルを製造し、これを減圧下
にメタノールを留去しながら熱分解し、含ケイ素
イソシアン酸エステルを得る方法（USP3494951
号）が知られている。しかしながら、前者のハロ
シリル塩誘導体を用いる方法では分解反応後の残
渣のシランの処理が問題となり、またカルバミン
酸メチルエステルを用いる方法では熱分解を高温
で実施しなければならず、生成するイソシアン酸
エステルが分解するといつた問題を有している。
この他にイソシアン酸エステルを製造する最も
一般的な方法として、ホスゲンやホスゲンの２量
体を用いる方法（特開昭61−145188号）が提案さ
れているが、ホスゲンやホスゲン２量体は法令で
その移動が禁止されており、当業者が常時、任意
の場所でホスゲン等を入手してイソシアン酸エス
テル類を製造することはできず、この点がホスゲ
ンやホスゲン２量体を原料として使用する製造法
の問題点となつている。
本発明は上記事情に鑑みなされたもので、シラ
ン処理や高温での熱分解を実施することもなく、
また、有毒なホスゲン等を原料とすることもない
ので安全衛生上からも優れ、しかも好収率で効率
よく容易に実施できる含ケイ素イソシアン酸エス
テルの製造方法を提供することを目的とする。
問題点を解決するための手段及び作用
本発明者らは、上記目的を達成するため鋭意検
討を進めた結果、クロル蟻酸エステル等のハロゲ
ノ蟻酸エステルと一般式(1)
で表わされる含ケイ素アルキルアミンとを反応さ
せて含ケイ素カーバメイト誘導体を合成した後、
これを熱分解する方法が一般式(2)
で表わされる含ケイ素イソシアン酸エステルを製
造する方法として有効であることを知見したが、
この場合、含ケイ素カーバメイト誘導体を熱分解
する際に、下記反応式
に示したようにカルバミン酸エステルが加熱によ
り平衡的にイソシアン酸エステルとアルコール類
とに分解し、カルバミン酸エステルへの逆反応に
より、含ケイ素イソシアン酸エステルが効率よく
得られないことを知見した。このため、更に検討
を行なつた結果、上記熱分解反応の際にトリアル
キルクロルシランを加え、生成するアルコール類
をトリアルキルシリル化することにより、アルコ
ール類が不活性化され、カルバミン酸エステルへ
の逆平衡反応が抑制され、イソシアン酸エステル
が収率よく合成されることを見い出した。
即ち、下記反応式
に示したように、例えばハロゲノ蟻酸エステルと
してクロル蟻酸フエニルを使用し、含ケイ素アル
キルアミンを含ケイ素カーバメイトに変えた後、
この含ケイ素カーバメイトを熱分解して含ケイ素
イソシアン酸エステルとする際に、例えばトリメ
チルクロルシラン等のトリアルキルクロルシラン
の存在下に熱分解反応を行なわせることにより、
同時に生成するフエノールがナリメチルクロルシ
ランで捕捉され、得られたPhOSiMe3が平衡反応
に対し不活性となるので、フエノールが平衡的に
不活性化して生成物が含ケイ素カーバメイトへ逆
反応することが効果的に抑制され、収率よく含ケ
イ素イソシアン酸エステルが製造し得ることを知
見し、本発明をなすに至つたものである。
従つて、本発明はハロゲノ蟻酸エステルと、一
般式(1)
（但し、式中R1，R2及びR3は炭素数１〜５の
同一もしくは異なる炭化水素基又はアルコキシ基
を示し、R1，R2及びR3のうち少なくとも１つは
アルコキシ基である。）
で表わされる含ケイ素アルキルアミンとを反応さ
せて含ケイ素カーバメイト誘導体を合成した後、
トリアルキルクロルシランの存在下に該含ケイ素
カーバメイト誘導体を熱分解することを特徴とす
る一般式(2)
（但し、式中R1，R2及びR3は前記と同じ意味
を有する。）
で表わされる含ケイ素イソシアン酸エステルの製
造方法を提供するものである。
以下、本発明を更に詳しく説明する。
本発明の含ケイ素イソシアン酸エステルの製造
方法は、まず第１段階としてハロゲノ蟻酸エステ
ルと含ケイ素アルキルアミンとを反応させて含ケ
イ素カーバメイトを製造し、次に第２段階として
この含ケイ素カーバメイトをトリアルキルクロル
シランの存在下で熱分解するものである。
この場合、本発明の第１段階の反応で使用する
(1)式の含ケイ素アルキルアミン
INDUSTRIAL APPLICATION FIELD The present invention relates to a method for producing a silicon-containing isocyanate ester having an alkoxysilyl group as a functional group in the molecule, and more specifically, to a silicon-containing carbamate ester from a halogenoformate and a silicon-containing alkylamine. In addition, when the silicon-containing carbamate is heated to produce the silicon-containing isocyanate, the alcohols produced at the same time are trialkylsilylated to suppress the back reaction to the silicon-containing carbamate. The present invention relates to a method for advantageously producing silicon isocyanate esters. BACKGROUND ART AND PROBLEMS TO BE SOLVED BY THE INVENTION Silicon-containing isocyanate esters are useful as polymer-modifying materials and are attracting attention as materials that can easily introduce alkoxy groups into polymers. As a method for producing this silicon-containing isocyanate ester, a method is conventionally known in which a silane compound and allyl isocyanate are subjected to a hydrosilylation reaction in the presence of rhodium trichloride (Japanese Patent Publication No. 55-40592 issue). However, this method uses allyl isocyanate, which is highly toxic, as a starting material and has various safety problems in terms of handling. Another example of a production method is a method in which a halosilyl salt derivative of carbamic acid is produced using a silicon-containing alkylamine as a starting material, and this is decomposed to obtain a silicon-containing isocyanate ester (Japanese Patent Publication No.
57020), and a method of producing methyl carbamate from a silicon-containing alkylamine and thermally decomposing it under reduced pressure while distilling methanol off to obtain a silicon-containing isocyanate ester (USP 3494951).
No.) is known. However, in the former method using halosilyl salt derivatives, treatment of the silane residue after the decomposition reaction becomes a problem, and in the method using carbamate methyl ester, thermal decomposition must be carried out at high temperature, resulting in isocyanate esters produced. The problem is that it breaks down. In addition, as the most common method for producing isocyanate esters, a method using phosgene or phosgene dimer has been proposed (Japanese Patent Application Laid-open No. 145188/1988), but phosgene and phosgene dimer are The movement of phosgene is prohibited, and it is not possible for those skilled in the art to obtain phosgene etc. from any location at any time to produce isocyanate esters.This point makes it difficult to use phosgene or phosgene dimer as a raw material. This has become a problem in the manufacturing method. The present invention was made in view of the above circumstances, and does not require silane treatment or thermal decomposition at high temperatures.
Another object of the present invention is to provide a method for producing a silicon-containing isocyanate ester, which is excellent in terms of safety and hygiene since no toxic phosgene or the like is used as a raw material, and which can be carried out efficiently and easily with a good yield. Means and Effects for Solving the Problems In order to achieve the above object, the present inventors have carried out intensive studies and found that halogenoformates such as chloroformates and general formula (1) After synthesizing a silicon-containing carbamate derivative by reacting with a silicon-containing alkylamine represented by
The method for thermally decomposing this is the general formula (2) It was found that this method is effective as a method for producing silicon-containing isocyanate ester represented by
In this case, when thermally decomposing a silicon-containing carbamate derivative, the following reaction formula is used: As shown in Figure 2, it was discovered that carbamate ester decomposes into isocyanate ester and alcohol in an equilibrium manner by heating, and silicon-containing isocyanate ester cannot be obtained efficiently due to the reverse reaction to form carbamate ester. Therefore, as a result of further investigation, we found that by adding trialkylchlorosilane during the above thermal decomposition reaction and trialkylsilylating the alcohols produced, the alcohols are inactivated and converted into carbamate esters. It was discovered that the reverse equilibrium reaction of isocyanate was suppressed and isocyanate esters were synthesized in good yield. That is, the following reaction formula As shown in , for example, phenyl chloroformate is used as a halogenoformic acid ester, and after converting a silicon-containing alkylamine to a silicon-containing carbamate,
When thermally decomposing this silicon-containing carbamate to form a silicon-containing isocyanate ester, for example, by carrying out a thermal decomposition reaction in the presence of a trialkylchlorosilane such as trimethylchlorosilane,
The phenol produced at the same time is captured by nalimethylchlorosilane, and the resulting PhOSiMe 3 becomes inert to the equilibrium reaction, so that the phenol is inactivated in an equilibrium manner and the product back-reacts to silicon-containing carbamate. The inventors have discovered that silicon-containing isocyanate esters can be effectively suppressed and produced in good yield, leading to the present invention. Therefore, the present invention provides a halogenoformic acid ester and a compound of the general formula (1). (However, in the formula, R 1 , R 2 and R 3 represent the same or different hydrocarbon groups or alkoxy groups having 1 to 5 carbon atoms, and at least one of R 1 , R 2 and R 3 is an alkoxy group. After synthesizing a silicon-containing carbamate derivative by reacting with a silicon-containing alkylamine represented by
General formula (2) characterized in that the silicon-containing carbamate derivative is thermally decomposed in the presence of trialkylchlorosilane (However, in the formula, R 1 , R 2 and R 3 have the same meanings as above.) A method for producing a silicon-containing isocyanate ester represented by the following is provided. The present invention will be explained in more detail below. In the method for producing a silicon-containing isocyanate ester of the present invention, first, in the first step, a halogenoformate and a silicon-containing alkylamine are reacted to produce a silicon-containing carbamate, and then, in the second step, this silicon-containing carbamate is reacted with a silicon-containing carbamate. It decomposes thermally in the presence of alkylchlorosilane. In this case, used in the first step reaction of the present invention
Silicon-containing alkylamine of formula (1)
３−（ジメトキシメチルシリル）プロピルアミ
ン152.8ｇ（0.8モル）とトリエチルアミン171.7ｇ
（1.7モル）とをトルエン300mlに溶解し、水冷却
により温度を20〜50℃の範囲に保ちながらこの溶
液中にクロル蟻酸フエニル128.7ｇ（0.82モル）
を滴下する。滴下終了後、温度を50〜60℃に昇温
し、３時間撹拌を続ける。更に温度を60℃から
徐々に上げながらトリメチルクロルシラン87.2ｇ
（0.8モル）を滴下する。トリメチルクロルシラン
滴下終了後、温度を90〜100℃に保ちながら３時
間撹拌を続け、反応を完了させた。反応終了後、
生成したトリエチルアミン塩酸塩を別し、液
を得た。このトリエチルアミン塩酸塩を500mlの
水で処理し、生じた有機層を水層より手早く分離
し、Na2SO4を用いて乾燥した後、最初の液に
合併する。この液を減圧蒸留したところ、トル
エン及び副生物のトリメチルフエノキシシランが
最初に留出し、その後沸点86〜87℃／３mmHgの
留分としてイソシアン酸３−（ジエトキシメチル
シリル）プロピル139ｇ（収率80％）が留出した。
〔実施例 ２〜４〕
実施例１の３−（ジエトキシメチルシリル）プ
ロピルアミンの代わりに３−（トリエトキシシリ
ル）プロピルアミン、３−（ジメトキシメチルシ
リル）プロピルアミン、３−（トリメトキシシリ
ル）プロピルアミンをそれぞれ用い、実施例１と
同様にして対応するイソシアン酸エステル
152.8 g (0.8 mol) of 3-(dimethoxymethylsilyl)propylamine and 171.7 g of triethylamine
(1.7 mol) was dissolved in 300 ml of toluene, and 128.7 g (0.82 mol) of phenyl chloroformate was added to this solution while keeping the temperature in the range of 20 to 50°C by cooling with water.
drip. After the dropwise addition is completed, the temperature is raised to 50-60°C and stirring is continued for 3 hours. Furthermore, 87.2g of trimethylchlorosilane was added while gradually increasing the temperature from 60℃.
(0.8 mol) was added dropwise. After the addition of trimethylchlorosilane was completed, stirring was continued for 3 hours while maintaining the temperature at 90 to 100°C to complete the reaction. After the reaction is complete,
The generated triethylamine hydrochloride was separated to obtain a liquid. The triethylamine hydrochloride is treated with 500 ml of water, and the resulting organic layer is quickly separated from the aqueous layer, dried over Na 2 SO 4 and then combined with the first liquid. When this liquid was distilled under reduced pressure, toluene and the by-product trimethylphenoxysilane were distilled out first, and then 139 g of 3-(diethoxymethylsilyl)propyl isocyanate was obtained as a fraction with a boiling point of 86-87°C/3 mmHg. 80%) was distilled out. [Examples 2 to 4] 3-(triethoxysilyl)propylamine, 3-(dimethoxymethylsilyl)propylamine, 3-(trimethoxysilyl) instead of 3-(diethoxymethylsilyl)propylamine in Example 1 ) The corresponding isocyanate esters were prepared in the same manner as in Example 1 using propylamine.
【式】を合成した。 結果を下記表に示す。[Formula] was synthesized. The results are shown in the table below.
【表】
〔実施例 ５〕
実施例１のトリエチルアミンの代わりにピリジ
ンを用いた以外は実施例１と同様にして反応を行
なつた。イソシアン酸３−（ジエトキシメチルシ
リル）プロピルを76％の収率で得た。[Table] [Example 5] A reaction was carried out in the same manner as in Example 1 except that pyridine was used in place of triethylamine. 3-(diethoxymethylsilyl)propyl isocyanate was obtained in a yield of 76%.
１ 式
式中
R1 R2
（8S）−８−フルオロエリスロ
マイシン Ａ OH
CH3
（8S）−８−フルオロエリスロ
マイシン Ｂ Ｈ
CH3
（8S）−８−フルオロエリスロ
マイシン Ｃ OH
Ｈ
（8S）−８−フルオロエリスロ
マイシン Ｄ Ｈ
Ｈ
を有する（8S）−８−フルオロエリスロマイシン
類を製造する方法であつて、
1 formula In the formula R 1 R 2 (8S)-8-fluoroerythromycin A OH CH 3 (8S)-8-fluoroerythromycin B H CH 3 (8S)-8-fluoroerythromycin C OH H (8S)-8-fluoroerythromycin D A method for producing (8S)-8-fluoroerythromycins having H H , the method comprising:
Claims (1)
ンとの反応を第３級アミンの存在下で行なうと共
に、含ケイ素カーバメイト誘導体の熱分解を第３
級アミンの存在下で行なうようにした特許請求の
範囲第１項記載の製造方法。 ３ ハロゲノ蟻酸エステルとしてクロル蟻酸エス
テルを使用するものである特許請求の範囲第１項
又は第２項記載の製造方法。2. The reaction between the chloroformate and the silicon-containing alkylamine is carried out in the presence of a tertiary amine, and the thermal decomposition of the silicon-containing carbamate derivative is carried out in the presence of a tertiary amine.
2. The manufacturing method according to claim 1, which is carried out in the presence of a grade amine. 3. The manufacturing method according to claim 1 or 2, wherein a chloroformate is used as the halogenoformate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8344087A JPS63250391A (en) | 1987-04-03 | 1987-04-03 | Production of silicon-containing isocyanic acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8344087A JPS63250391A (en) | 1987-04-03 | 1987-04-03 | Production of silicon-containing isocyanic acid ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63250391A JPS63250391A (en) | 1988-10-18 |
| JPH0312076B2 true JPH0312076B2 (en) | 1991-02-19 |
Family
ID=13802484
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8344087A Granted JPS63250391A (en) | 1987-04-03 | 1987-04-03 | Production of silicon-containing isocyanic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63250391A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5218133A (en) * | 1992-08-20 | 1993-06-08 | Union Carbide Chemicals & Plastics Technology Corporation | Process for making a silylisocyanurate |
| DE102010061816A1 (en) * | 2010-11-23 | 2012-05-24 | Wacker Chemie Ag | Process for the preparation of carbamatoorganosilanes |
| JP6167936B2 (en) * | 2014-02-26 | 2017-07-26 | 信越化学工業株式会社 | Method for producing cyclic silazane compound |
| CN109232638A (en) * | 2018-11-16 | 2019-01-18 | 大连鼎燕医药化工有限公司 | A method of preparing 3- isocyanate group propyl trimethoxy silicane |
-
1987
- 1987-04-03 JP JP8344087A patent/JPS63250391A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63250391A (en) | 1988-10-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5886205A (en) | Process for producing silicon-containing isocyanate compound | |
| JP2009508856A (en) | Method for producing isocyanatosilane | |
| JP2000026609A (en) | Preparation of alkoxy group-terminated polydiorganosiloxane | |
| JP3651572B2 (en) | Process for producing partially added cyclic organohydrogensiloxane | |
| JPH0813826B2 (en) | Thexyltrialkoxysilane | |
| EP0639576A1 (en) | Organopolysiloxanes having a silanol group and process of making them | |
| JPH0312076B2 (en) | ||
| JP5652829B2 (en) | Method for producing silanol under anhydrous conditions | |
| US4496754A (en) | Silyl carbamates and synthesis thereof | |
| JP3507963B2 (en) | Method for producing 1,3-bis (3-aminopropyl) -1,1,3,3-tetraorganodisiloxane | |
| JPH03197486A (en) | Production of organosiloxane having alkoxysilyl group | |
| JPH058713B2 (en) | ||
| JP2612996B2 (en) | Method for producing isocyanurate containing organosilicon group | |
| JPS6221352B2 (en) | ||
| JP3666549B2 (en) | Method for producing 1,3-bis (3-aminopropyl) tetramethyldisiloxane | |
| JP3972162B2 (en) | Process for producing isocyanato group-containing organosilicon compounds | |
| JP3137439B2 (en) | 1-aza-2-silacyclobutane compound and method for producing the same | |
| JP2002020392A (en) | N-alkenylazasilacyclopentane and method for producing the same | |
| US5136072A (en) | Thexyl C1 -C4 alkyl dialkoxy silane | |
| JPH07285974A (en) | Production of cyclotetrasiloxane | |
| JP2002193976A (en) | Production method of n-substituted-3-silylpropylamine and its derivative | |
| JP2797962B2 (en) | Cycloalkyl (2-norbornyl) dialkoxysilane compound | |
| JPH06107671A (en) | Organosilicon compound and its production | |
| JP3815535B2 (en) | Method for silylation of alcohols | |
| US4663471A (en) | Method for the preparation of N-methyl-N-trimethylsilyl trifluoroacetamide |