TW584628B - Process for preparation of fluorine-containing carbonyl compounds - Google Patents
Process for preparation of fluorine-containing carbonyl compounds Download PDFInfo
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- TW584628B TW584628B TW91114439A TW91114439A TW584628B TW 584628 B TW584628 B TW 584628B TW 91114439 A TW91114439 A TW 91114439A TW 91114439 A TW91114439 A TW 91114439A TW 584628 B TW584628 B TW 584628B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/54—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of compounds containing doubly bound oxygen atoms, e.g. esters
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/287—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
584628 A7 ___B7_ 五、發明説明(1 ) 發明的技術領域 (請先閱讀背面之注意事項再填寫本頁) 本發明係關於一種有效率地製造具有種種構造的含氟 羰基化合物之方法。 發明的技術背景 已知分子量1000以上的聚乙二醇與三氟醋酸進行反應 後’液相中經氟化得到末端具有三氟甲基的聚乙二醇之反 應(特表平4-500520號)。又,經特表平4-500520的方法 製造出之具有三氟甲基的聚乙二醇,於液相中氟化,分解 經全氟化的聚乙二醇二甲酯之2個酯鍵,得到經全氟化的 二醯基氟化物之方法爲已知(US 5466877 )。 又,本發明人已提出有關,作爲由非氟的醇中得到含 氟羰基化合物的方法,非氟的醇中,反應含氟的單醯基氟 化物所得到之部分氟化酯,與氟反應得到全氟化酯後,進 行該酯的分解反應之方法(WOOO/56694 )申請案。 經濟部智慧財產局員工消費合作社印製 US5466877所記載的酯鍵之分解反應中,雖會生成 CFsCOF,但因CF3C〇F爲低沸點(-59°C )故較難回收,而 無有關實際回收之記載。又,該方法中,必須準備對應含 氟醯基氟化物的化合物之含氟羰酸(例如三氟醋酸),但 一般而言含氟羰基化合物爲高價物,可購入的結構受到限 制。 WOOO/56694的方法,係爲非氟的醇與1倍莫耳的含氟 單醯基氟化物進行反應的方法,但含氟單醯基氟化物一般 而言爲高價物,故有著成本高之問題。較爲經濟的方法爲 使用低分子量的含氟單醯基氟化物之方法,但低分子量的 本紙張尺度適用中.國國家標準(CNS ) A4規格(210X297公瘦) 584628 A7 ___B7_ 五、發明説明(2 ) 含氟之單醯基氟化物因其爲低沸點,故經酯分解反應後難 以回收,而有著因回收及再利用之無經濟價値的問題。 (請先閱讀背面之注意事項再填寫本頁) 且,採用低分子量的含氟之單醯基氟化物時,部分氟 化酯的蒸氣壓會提高,於液相氟化反應中會隨著氣體而引 起氣相部分的反應。氣相部分的反應有著反應較難控制, 回收率較爲低之問題。另一方面,欲降低部分氟化酯的蒸 氣壓,所使用的高分子量的部分氟化酯之方法,有著部分 氟化酯的種類較爲少、價位高、經濟價値低等問題。 發明的揭示 本發明提供解決上述課題之下述製造方法。 經濟部智慧財產局員工消費合作社印製 1·一種含氟羰基化合物之製造方法,其特徵爲式1所 表示的化合物與式2所表示的化合物進行酯化反應,得到 含有1種以上如式3所表示的化合物之酯化反應生成物, 該酯化反應生成物經氟化反應成爲全氟化後,得到含有1 種以上如式4所表示的氟化反應生成物,進行對該氟化反 應生成物的酯鍵之分解反應,得到含有式5所表示的化合 物與式2所表示的化合物之分解反應生成物,由該分解反 應生成物得到含有式5所表示的含氟羰基化合物者, R^HR'OH……式1 Qf(COF)n……式2 Qf(COOCHR1R2)m(COF)n.m……式 3 Qf(COOCFRlfR2f)m(COF)n.m……式 4 RlfC〇R2f····..式 5 惟,式中的符號如下述所示, 本紙張尺度適用中.國國家標準(CNS ) A4規格(210X297公釐) 77^ ' 584628 經濟部智慧財產局員工消費合作社印製 A7 ___B7__五、發明説明(3 ) R1、R2 : R1表示氫原子或經氟化的1價有機基,R2表 示經氟化的1價有機基,R1與R2可同時經氟化而形成2價 有機基, RH'R^R1表示氫原子時的Rlf爲氟原子、R1表示1 價有機基時的尺"爲R1經全氟化之1價有機基,尺”爲R2經 全氟化之1價有機基,惟,R1與R2同時經氟化而形成2價 有機基時,尺^與11〃同時形成2價有機基經全氟化之基, Qf :經全氟化之η價有機基、 η : 2以上的整數、 m : 2以上且η以下的整數。 2. 如申請專利範圍第1項之製造方法,其中與式1所表 示的化合物進行反應之如式2所表示的化合物,係由酯鍵 的分解反應生成物所得之式2所表示的化合物。 3. 如申請專利範圍第1項或第2項之製造方法,其中式 1所表示的化合物之分子量爲32〜200,酯化反應生成物的 平均氟含量爲20〜60質量%,且酯化反應生成物的分子量 爲200〜1100者。 4·如申請專利範圍第1、2或3項之製造方法,其中 氟化反應爲液相氟化反應。 5·如申請專利範圍第1項至第4項中任一項之製造方法 ,其中如式2所表示的化合物爲式(2-1 )所表示的化合物 ,酯化反應生成物必須有式(3-1 )所表示的化合物,氟化 反應生成物係以式(4-1 )所表示的化合物爲必須者,分解 反應生成物係以式(5-1)所表示的化合物與式(2-1)所袠 本紙張尺度適用中國國家標準(CNS ) Α4規格(210X297公釐) Tfil ' 〜 (請先閲讀背面之注意事項再填寫本頁) 裝· 訂 .加 584628 A7 ____B7 五、發明説明(4 ) 不的化合物爲必須者,含氟羰基化合物爲式(5 -1 )所表示 的化合物, (請先閲讀背面之注意事項再填寫本頁) FC〇Qf2C〇F.·····式(2-1) R^HR'OCOQ^COOCHR^2..·.··式(3-1) RlfCFR2f〇C〇Qf2C〇〇CFRlfR2f ·.··.·式(4-1)584628 A7 ___B7_ V. Description of the Invention (1) Technical Field of the Invention (Please read the notes on the back before filling out this page) The present invention relates to a method for efficiently producing fluorine-containing carbonyl compounds with various structures. Technical background of the invention It is known that after reacting polyethylene glycol having a molecular weight of 1,000 or more with trifluoroacetic acid, the reaction of fluorination in the liquid phase to obtain a polyethylene glycol having a trifluoromethyl terminal at the end (see Table No. 4-500520) ). In addition, a polyethylene glycol having a trifluoromethyl group manufactured by the method of Table 4-500520 is fluorinated in a liquid phase to decompose the two ester bonds of the perfluorinated polyethylene glycol dimethyl ester. A method for obtaining a perfluorinated difluorenyl fluoride is known (US 5466877). In addition, the present inventors have proposed that, as a method for obtaining a fluorinated carbonyl compound from a non-fluorinated alcohol, a partially fluorinated ester obtained by reacting a fluorine-containing monofluorenyl fluoride in a non-fluorinated alcohol and reacted with fluorine After the perfluorinated ester is obtained, a method for decomposing the ester (WOOO / 56694) is applied. In the decomposition reaction of the ester bond described in US5466877 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, although CFsCOF is formed, it is difficult to recover CF3COF because of its low boiling point (-59 ° C) without actual recycling Of the record. In this method, a fluorinated carbonyl acid (for example, trifluoroacetic acid) corresponding to a fluorinated fluorinated fluoride-containing compound must be prepared, but in general, the fluorinated carbonyl compound is a high-priced product, and the structure that can be purchased is limited. The method of WOOO / 56694 is a method in which a non-fluorine alcohol is reacted with 1 times mole of a fluorine-containing monofluorenyl fluoride. However, the fluorine-containing monofluorinated fluoride is generally a high-value compound, so it has a high cost. problem. The more economical method is a method using a low molecular weight fluorine-containing monofluorinated fluoride, but the paper size of the low molecular weight is applicable. National National Standard (CNS) A4 specification (210X297 male thin) 584628 A7 ___B7_ 5. Description of the invention (2) Because of its low boiling point, the fluorine-containing monofluorenyl fluoride is difficult to recover after the ester decomposition reaction, and it has the problem of no economic value due to recovery and reuse. (Please read the precautions on the back before filling in this page.) Moreover, when using low molecular weight fluorine-containing monofluorenyl fluoride, the vapor pressure of some fluorinated esters will increase. Instead, a gas phase reaction is caused. The reaction in the gas phase has the problems that the reaction is difficult to control and the recovery rate is low. On the other hand, in order to reduce the vapor pressure of partially fluorinated esters, the method of partially fluorinated esters of high molecular weight used has problems such as relatively few types of partially fluorinated esters, high price, and low economic value. Disclosure of the Invention The present invention provides the following manufacturing method that solves the above-mentioned problems. Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1. A method for producing a fluorocarbonyl compound, characterized in that the compound represented by Formula 1 and the compound represented by Formula 2 are esterified to obtain one or more compounds such as Formula 3 An esterification reaction product of the indicated compound. After the esterification reaction product is converted to perfluorination by a fluorination reaction, one or more fluorination reaction products represented by Formula 4 are obtained, and the fluorination reaction is performed. Decomposition reaction of the ester bond of the product to obtain a decomposition reaction product containing the compound represented by Formula 5 and the compound represented by Formula 2, and from the decomposition reaction product to obtain a fluorine-containing carbonyl compound represented by Formula 5, R ^ HR'OH ... Formula 1 Qf (COF) n ... Formula 2 Qf (COOCHR1R2) m (COF) nm ... Formula 3 Qf (COOCFRlfR2f) m (COF) nm ... Formula 4 RlfC〇R2f ... .. Formula 5 However, the symbols in the formula are as shown below. This paper size is applicable. National Standard (CNS) A4 (210X297 mm) 77 ^ '584628 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ___B7_ V. Description of the invention (3) R1, R2: R1 represents hydrogen Or fluorinated monovalent organic group, R2 represents a fluorinated monovalent organic group, R1 and R2 can be fluorinated to form a divalent organic group at the same time, RH'R ^ R1 represents a hydrogen atom when Rlf is fluorine Atom, R1 represents a monovalent organic group. "R1 is a monovalent organic group with R1 perfluorinated, and" R "is a monovalent organic group with R2 perfluorinated. However, R1 and R2 are formed by fluorination at the same time. In the case of a divalent organic group, the ^^ and 11〃 simultaneously form a divalent organic group that is perfluorinated, Qf: a perfluorinated η-valent organic group, η: an integer of 2 or more, and m: 2 or more and η or less 2. The manufacturing method according to item 1 of the scope of patent application, wherein the compound represented by formula 2 which reacts with the compound represented by formula 1 is represented by formula 2 obtained from the decomposition reaction product of an ester bond. 3. The manufacturing method according to item 1 or 2 of the scope of patent application, wherein the molecular weight of the compound represented by Formula 1 is 32 to 200, and the average fluorine content of the esterification reaction product is 20 to 60% by mass. And the molecular weight of the esterification reaction product is 200 ~ 1100. 4. If the manufacturing method of the scope of patent application No. 1, 2 or 3, The intermediate fluorination reaction is a liquid phase fluorination reaction. 5. The manufacturing method according to any one of claims 1 to 4 in the scope of application for a patent, wherein the compound represented by formula 2 is represented by formula (2-1) The compound and the esterification reaction product must have a compound represented by the formula (3-1). The fluorination reaction product is based on the compound represented by the formula (4-1). The decomposition reaction product is based on the formula (5). -1) The compound represented by the formula and formula (2-1) The size of the paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) Tfil '~ (Please read the precautions on the back before filling this page) · Order. Add 584628 A7 ____B7 V. Description of the invention (4) The compound that is not necessary is a fluorinated carbonyl compound is the compound represented by formula (5 -1), (Please read the precautions on the back before filling this page) FC〇Qf2C〇F ..... Formula (2-1) R ^ HR'OCOQ ^ COOCHR ^ 2 ..... Formula (3-1) RlfCFR2f〇C〇Qf2C〇CFRlfR2f ... . · Formula (4-1)
RlfCOR2f……式(5-1) 惟,式中的符號如下述所示, R1、R2、Rlf、R2f :與上述相同意義,RlfCOR2f ... Formula (5-1) However, the symbols in the formula are as follows, R1, R2, Rlf, R2f: the same meaning as above,
Qf2 :經全氟化的2價有機基。 6. 如申請專利範圍第5項之製造方法,其中酯化反應生 成物爲,與式(3-1)所表示的化合物同時含有式(3-1H) 所表示的化合物,氟化反應生成物爲,與式(4-1 )所表示 的化合物同時含有式(4-1H)所表示的化合物,Qf2: Divalent organic group perfluorinated. 6. The manufacturing method according to item 5 of the scope of patent application, wherein the esterification reaction product is a compound represented by formula (3-1H) and a compound represented by formula (3-1H), and a fluorination reaction product To contain the compound represented by formula (4-1H) together with the compound represented by formula (4-1),
RlCHR2OCOQf2COF..^ (3-1H)RlCHR2OCOQf2COF .. ^ (3-1H)
RlfCFR2fOCOQf2COF..^i (4-1H) 惟,式中R1、R2、Rlf、R2f及Qf2表示與上述相同意義 ο 經濟部智慧財產局員工消費合作社印製 7. 如申請專利範圍第5項或第6項之製造方法,其中使 酯化反應生成物中含下述式(3-2Η )所表示的化合物,進 行氟化反應者, R^HR^COQ^COOCHR^2...^ (3-2H), 惟, R1、R2 :與上述相同意義, QH2 :必須有氫原子的2價有機基,且經全氟化形成Qf2 本紙張尺度適用中國國家標準(CNS ) A4規格(210 X 297公釐) -7 - 584628 Α7 Β7 五、發明説明(5 ) 的基。 (請先閲讀背面之注意事項再填寫本頁) 8.如申請專利範圍第7項之製造方法,其中對於式(3-1)所表示的化合物,於超過〇質量%而質量%以下之 式(3-2H)所表示的化合物存在下,進行氟化反應者。 9·如申請專利範圍第7項或第8項之製造方法,其中 R1 與 R2 爲-CH3,Rlf 與 R2f 爲<?3、Qf2 爲-(CF2) k_ (惟,k 表示2〜8的整數),且QH2爲-(CH2) ,或R1爲-Η、R2 爲-CH ( CH〇 2、尺”爲冲、( CF〇 2,且 QH2 爲 -(CH2) k-0 10.如申請專利範圍第5項至第9項中任一項之製造方 法’其中液相氟化中的液相爲,係以式(4-1 )所表示的化 合物及/或式(5-1)所表示的化合物爲必須者。 11·如申請專利範圍第1項至第1〇項中任一項之製造 方法’其中式1所表示的化合物與式2所表示的化合物進 行酯化反應中,式(1 )所表示的化合物量爲式2所表示的 化合物之0.5〜1倍莫耳。 經濟部智慧財產局員工消費合作社印製 12·如申請專利範圍第1項至第11項中任一項之製造 方法,其中式3所表示的化合物之氟化反應中,具有對應 化合物(3)的同一碳骨架,且比化合物(3)含較少氟量 之化合物存在下,進行氟化反應者。 13.—種化合物,其爲如下述式所表示的任意化合物。 (CH3)2CH〇C〇(CF〇4CO〇CH(CH3)2、 (CF3)2CF〇C〇(CF2)4C〇〇CF(CF3)2、 (CH3)2CHCH2〇C〇(CF〇2C〇〇CH2CH(CH3)2、 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) :> 7' Η 584628 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明(6 ) (CF3)2CFCF2〇C〇(CF2)2C〇〇CF2CF(CF3)2、 (CH3)2CHCH2〇C〇(CF2)3C〇〇CH2CH(CH3)2、 (CF3)2CFCF2〇C〇(CF〇3C〇〇CF2CF(CF3)2。 實施發明的最佳型態 本發明中的有機基爲必須有碳原子之基。作爲經氟化 的有機基,可舉出具有C-H部分的有機基、或具有碳-碳不 飽和鍵結之有機基,以具有C-H部分的有機基爲佳,特別 爲該基之中碳·碳鍵結僅以單鍵所成飽和有機基爲佳。 作爲具有C-H部分的有機基,以飽和烴基、含有醚性 氧原子的飽和烴基、部分鹵化飽和烴基、或部分鹵化(含 有醚性氧原子的飽和烴基)基爲佳。所謂該部分鹵化,意 味著以氫原子剩餘比率進行鹵化者。作爲鹵素原子,可舉 出氟原子、氯原子、溴原子、或碘原子,以氟原子或氯原 子爲佳。特別作爲部分鹵化之基的鹵素原子而言以氯原子 爲佳。 作爲1價烴基,可舉出烷基、環烷基、或具有環部分 的1價飽和烴基(例如,環烷基、環烷基烷基、或這些基 作爲部分結構的基)等,以烷基爲佳。 作爲2價烴基,可舉出伸烷基、環伸烷基、或具有環 部分的2價飽和烴基(例如環烷基、雙環烷基、或環伸院 基作爲部分結構之2價飽和脂肪族烴基。)等,以伸院基 爲佳。 作爲含有醚性氧原子的飽和烴基中的1價之基,可舉 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -9 - I--------|^批衣----„---1T------0 (請先閱讀背面之注意事項再填寫本頁) 584628 A7 B7 五、發明説明(7 ) (請先閱讀背面之注意事項再填寫本頁) 出碳-碳鍵結間插入醚性氧原子之烷基、或碳-碳鍵結間插入 醚性氧原子之環烷基等。又,作爲含有醚性氧原子的飽和 烴基中的2價之基,可舉出碳-碳鍵結間或該基的鍵結末端 插入醚性氧原子之伸烷基、或碳-碳鍵結間插入醚性氧原子 之環伸烷基等,特別爲氧基伸烷基、或具有聚氧基伸烷基 部分的基爲佳。含有醚性氧原子的基中,醚性氧原子的數 目可爲1個或2個以上。 所謂全氟化,係將欲氟化的基中所存在的欲氟化的部 分,實際全部氟化者。例如,全氟化具有C-H部分的有機 基之基時,C-H部分實際上全成爲C-F者,存在碳-碳不飽 和鍵結的有機基經全氟化之基,係指實際上全部的不飽和 鍵結上附加氟原子者。 經濟部智慈財產局員工消費合作社印製 作爲經全氟化的1價有機基,可舉出全氟化烷基,具 體而言可舉出-CF2CF3、-CF2CF2CF3、-CFaCFaCFiCF;、 -CF2CC1F2-、CF2CBrF2、或-CF2 CFC1 CF2C卜-CF ( CF3 ) 2、 -CF2CF ( CF3) 2、-CF ( CF3) CF2 CF3、-C ( CFO 3 等。作爲 經全氟化的2價有機基,可舉出全氟化伸烷基,具體而言 可舉出-CF2CF2CF2CF2-、-CF ( CF3) CF2CF2CF2-、 -CFaCF ( CF3) CF2CF2-等。又,作爲經全氟化的含有醚性氧 原子的基,可舉出這些基的碳-碳原子間插入醚性氧原子的 基。 本發明的製造方法之槪念,如下式所示。 本紙張尺度適用中.國國家標準(CNS ) A4規格(21〇X297公釐) 584628 A7 B7 五、發明説明(8 )RlfCFR2fOCOQf2COF .. ^ i (4-1H) However, in the formula, R1, R2, Rlf, R2f, and Qf2 represent the same meanings as above. Ο Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The production method according to item 6, wherein the esterification reaction product contains a compound represented by the following formula (3-2Η) and a fluorination reaction is performed, R ^ HR ^ COQ ^ COOCHR ^ 2 ... ^ (3- 2H), except that R1 and R2 have the same meaning as above, QH2: must have a divalent organic group of hydrogen atom, and be formed into Qf2 by perfluorination. The paper size is applicable to China National Standard (CNS) A4 (210 X 297) (Centi) -7-584628 Α7 Β7 5. The base of invention description (5). (Please read the precautions on the back before filling out this page) 8. The manufacturing method as described in item 7 of the scope of patent application, wherein the compound represented by formula (3-1) is more than 0 mass% and less than mass%. (3-2H) A fluorination reaction is performed in the presence of the compound represented by (3-2H). 9. If the manufacturing method of the 7th or 8th in the scope of patent application, where R1 and R2 are -CH3, Rlf and R2f are <? 3, Qf2 is-(CF2) k_ (However, k represents 2 ~ 8 Integer), and QH2 is-(CH2), or R1 is -Η, R2 is -CH (CH〇2, ruler "is punch, (CF〇2, and QH2 is-(CH2) k-0 10. The manufacturing method according to any one of claims 5 to 9, wherein the liquid phase in the liquid phase fluorination is the compound represented by the formula (4-1) and / or the compound represented by the formula (5-1) The compound represented is necessary. 11. The manufacturing method according to any one of claims 1 to 10 in the scope of the patent application, wherein the compound represented by formula 1 and the compound represented by formula 2 are subjected to an esterification reaction, (1) The amount of the compound represented is 0.5 to 1 mole of the compound represented by Formula 2. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 12. If any of the items 1 to 11 of the scope of patent application In a manufacturing method, in the fluorination reaction of the compound represented by Formula 3, in the presence of a compound having the same carbon skeleton as the corresponding compound (3) and containing less fluorine than the compound (3), A fluorination reactor. 13. A compound, which is any compound represented by the following formula: (CH3) 2CH0CO (CF04CO0CH (CH3) 2, (CF3) 2CF0CO (CF2) ) 4C〇〇CF (CF3) 2, (CH3) 2CHCH2〇C〇 (CF〇2C〇CH2CH (CH3) 2, this paper size applies Chinese National Standard (CNS) A4 specifications (210X297 mm):> 7 '' 584628 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (6) (CF3) 2CFCF2〇C〇 (CF2) 2C〇〇CF2CF (CF3) 2, (CH3) 2CHCH2〇C〇 (CF2 ) 3C0CH2CH (CH3) 2, (CF3) 2CFCF2OC0 (CF03C0CF2CF (CF3) 2. Best Mode for Carrying Out the Invention) The organic group in the present invention is a group which must have a carbon atom. Examples of the fluorinated organic group include an organic group having a CH portion or an organic group having a carbon-carbon unsaturated bond. An organic group having a CH portion is preferred, and particularly, carbon and carbon in the group The bond is preferably only a saturated organic group formed by a single bond. As the organic group having a CH moiety, a saturated hydrocarbon group, a saturated hydrocarbon group containing an etheric oxygen atom, a partially halogenated saturated hydrocarbon group, or a partially A halogenated (saturated hydrocarbon group containing etheric oxygen atom) group is preferred. The partial halogenation means halogenation at the remaining ratio of hydrogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Preferably, a fluorine atom or a chlorine atom is used. Particularly, a halogen atom as a partially halogenated group is preferably a chlorine atom. Examples of the monovalent hydrocarbon group include an alkyl group, a cycloalkyl group, and a monovalent saturated hydrocarbon group having a ring portion (for example, a cycloalkyl group, a cycloalkylalkyl group, or a group having these groups as a partial structure). Base is better. Examples of the divalent hydrocarbon group include a divalent alkyl group, a cycloalkylene group, or a divalent saturated hydrocarbon group having a cyclic portion (for example, a cycloalkyl group, a bicycloalkyl group, or a divalent saturated aliphatic group having a cycloalkyl group as a partial structure). Hydrocarbyl.), Etc., preferably Shenyuanji. As a monovalent group in a saturated hydrocarbon group containing etheric oxygen atoms, the Chinese paper standard (CNS) A4 (210X297 mm) can be applied to this paper size -9-I -------- | ^ batch Clothing ---- „-1T ------ 0 (Please read the precautions on the back before filling this page) 584628 A7 B7 V. Invention Description (7) (Please read the precautions on the back before filling (In this page) an alkyl group having an etheric oxygen atom inserted between carbon-carbon bonds, or a cycloalkyl group having an etheric oxygen atom inserted between carbon-carbon bonds. Also, as a saturated hydrocarbon group containing etheric oxygen atoms, Examples of the divalent group include an alkylene group having an etheric oxygen atom inserted between carbon-carbon bonds or at the terminal end of the group, or a cycloalkylene group having an ethereal oxygen atom inserted between carbon-carbon bonds. Particularly, an oxyalkylene group or a group having a polyoxyalkylene portion is preferred. Among the groups containing etheric oxygen atoms, the number of etheric oxygen atoms may be one or two or more. The so-called perfluorination is a The portion to be fluorinated in the group to be fluorinated is actually all fluorinated. For example, when the organic group having a CH portion is perfluorinated, the CH portion actually becomes C -F, organic radicals with carbon-carbon unsaturated bonds are perfluorinated groups, which means that virtually all unsaturated bonds have fluorine atoms attached to them. It is printed as: Examples of the perfluorinated monovalent organic group include a perfluorinated alkyl group, and specifically, -CF2CF3, -CF2CF2CF3, -CFaCFaCFiCF ;, -CF2CC1F2-, CF2CBrF2, or -CF2 CFC1 CF2C, -CF ( CF3) 2, -CF2CF (CF3) 2, -CF (CF3) CF2 CF3, -C (CFO 3, etc.) Examples of the perfluorinated divalent organic group include perfluorinated alkylene groups. Specifically, Examples include -CF2CF2CF2CF2-, -CF (CF3) CF2CF2CF2-, -CFaCF (CF3) CF2CF2-, etc. Examples of the perfluorinated ether-containing oxygen-containing group include carbon-carbon atoms of these groups An etheric oxygen atom is inserted between the groups. The idea of the manufacturing method of the present invention is shown in the following formula. The paper size is applicable. National Standard (CNS) A4 (21 × 297 mm) 584628 A7 B7 V. Invention Instructions (8)
(請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本發明的製造方法係爲進行酯化反應、氟化反應、及 酯鍵的分解反應。 對於啓始物質的化合物(1 ),本發明的方法爲化合物 (1 )的分子量較小時較爲有利之方法,故RtHR2-部分的 碳數爲3〜10爲佳,特佳爲3〜5。化合物(1)的分子量爲 32〜200爲佳,特佳爲60〜150,而以60〜120爲最佳。 化合物(1 )中,R1、R2分別爲經氟化的1價有機基時 ,以烷基、環氧基、烷氧基爲佳。R1與R2同時經氟化形成 2價有機基時,作爲該2價有機基而言,以伸烷基、或伸烷 基的碳-碳鍵結間插入1個以上的醚性氧原子的基爲佳。 又,作爲化合物(1 ),可便宜購得種種結構的醇化合 物,故以未含赢原子的化合物(即,氟含量爲0質量%的 化合物)者爲佳。 化合物(1 ),選擇使用具有對應作爲目的的含氟鑛基 化合物(5 )結構之結構的化合物。化合物(1 )中的Rl或 本紙張尺度適用中g|國家標準(CNS ) A4規格(2丨〇><297公釐) -11 - 584628 A7 _____B7_ 五、發明説明(9 ) (請先閱讀背面之注意事項再填寫本頁) R2碳骨架之排列,以含氟羰基化合物(5)的Rlf &尺”保持 。又’含氟羰基化合物(5 )作爲含氟1級醇的原料時,以 使用R2爲氫原子的化合物(1 )爲佳,含氟羰基化合物(5 )作爲含氟2級醇的原料時,以使用R2爲經氟化的1價有 機基的化合物(1 )爲佳。 本發明中,化合物(1 )與化合物(2 )進行酯化反應 。化合物(2 )係表示,經全氟化的η價有機基(Qf)之鍵 結點上,鍵結η個-COF所表示的基之化合物。η表示2以 上的整數。Qf表示經全氟化的η價飽和烴基、全氟化基( 含有醚性氧原子的η價飽和烴基)爲佳。該基(Qf)爲2價 的基(Qf2 )時,以全氟伸烷基、全氟(含有醚性氧原子的 伸烷基)基爲特佳。且作爲化合物(2 ),因 FC〇(CF2) kC〇F (k表示2〜8的整數)較易取傳,且反應 收率較高故佳。 經濟部智慧財產局員工消費合作社印製 本發明的製造方法,進行1次的化學量論上對於化合 物(2 )而言,可得到η倍莫耳的含氟羰基化合物(5 )。 又,可回收化合物(2 ),回收的化合物(2 )可多次利用 。回收化合物(2 )所使用的方法如後述。作爲化合物(2 )的具體例子,可舉出後述η爲2時的化合物(2-1)。 化合物(1 )與化合物(2 )的反應,可由公知的酯化 反應條件實施。酯化反應亦可於酯化反應溶劑的存在下實 施,但於酯化反應溶劑未存在下實施時由容積效率的觀點 來看較爲佳。 使用酯化反應溶劑時,以二氯甲烷、氯仿、三乙胺、 本纸張尺度適用中.國國家標準(CNS ) Α4規格(210X297公釐) -12 - 584628 A7 _ B7_ 五、發明説明(10 ) (請先閱讀背面之注意事項再填寫本頁) 或三乙胺與四氫呋喃的混合溶劑爲佳。使用酯化反應溶劑 時的量,對化合物(1 )與化合物(2 )的總量而言爲50〜 5〇〇質量%爲佳。 化合物(1)與化合物(2)的反應中,因會產生氟酸 (HF ),鹼金屬氟化物(NaF、KF爲佳)或三烷基胺等可 作爲HF捕捉劑存在於反應系中。HF捕捉劑於反應相關的 化合物爲對酸不安定之化合物時使用爲佳。又,不使用HF 捕捉劑時,於可氣化HF的反應溫度下進行反應,且HF與 氮氣同時排出反應系統之外爲佳。HF捕捉劑的量,對產生 HF的理論値而言爲1〜1 0倍莫耳程度爲佳。 經濟部智慧財產局員工消費合作社印製 該酯化反應係爲2官能以上的酸氟化物與1官能基的 醇之酯化反應。該酯化反應,極性高的2官能以上之醇與1 官能的酸氟化物之反應做比較時,其反應速度與反應成績 亦高。又,酯化反應後的生成物中殘留醇,如後述並不佳 。由上述可知,使用於酯化反應的化合物(1 )的量,對於 化合物(2)以η莫耳(η爲對應化合物(2)中的-COF所 表示的基數(η ))以下爲佳。使用超過η的化合物(1 ) 亦不合經濟,且酯化反應的反應生成物中,會殘留未反應 的化合物(1 )。該酯化反應生成物中殘留未反應的化合物 (1 )時,會引起對氟化反應不佳的反應。因此,使用於酯 化反應的化合物(1 )的量,以不會殘留於酯化反應生成物 中之量爲佳,亦可省略酯化反應生成物的純化。特別爲該 化合物(1 )的量以〇.5η倍〜η倍莫耳爲特佳,0.9η倍〜η 倍莫耳爲最佳。 本紙張尺度適用中.國國家標準(CNS ) Α4規格(210Χ297公釐) 771 一~ 584628 A7 B7 五、發明説明(11 ) 使用化合物(2 )的本發明的優點,特別於化合物(1 )的分子量較爲低時發揮。化合物(2 )因構造中具有2以 觚 (請先閱讀背面之注意事項再填寫本頁) 上的醯基氟化物基,化合物(2 )中2分子以上的化合物( 1)會起反應。其結果,與具有1個醯基氟化物基的化合物 中使化合物(1 )反應時做比較,因化合物(3 )的分子量 會較大,蒸氣壓較爲小,而較易控制液相氟化反應的反應 進行,收率亦較高,且對於容積效率而言亦較有利。 酯化反應的反應溫度之下限,一般以-50°C爲佳,上限 爲+ 1 00 °C及酯化溶劑的沸點中以較低溫者爲佳。又,該反 應的反應時間,對應原料的供給速度與實際反應的化合物 量做適當變更。反應壓力爲常壓〜2MPa (表壓,以下壓力 表示表壓)爲佳。 經濟部智慧財產局員工消費合作社印製 酯化反應的生成物,必須含有1種以上的化合物(3) 。化合物(3)中的R^RlQf及η,表示與上述同義。m 表示經酯化反應形成之基(-COOCHW)的個數,2以上 且η以下的整數。(n-m)表示未被酯化所剩的-COF基之 個數,(n-m)爲0時表示不存在化合物(2)的-COF基。 作爲化合物(3),可舉出(n-m)爲0的化合物,n>m的 化合物(即,化合物(2 )的2個以上-COF基雖會被酯化 ,但非全被酯化的化合物),這些量比無特別限制。 作爲本發明的酯化反應生成物,即經酯化反應所生成 的所有生成物,亦含有化合物(3 )之外的化合物,例如, 作爲酯化反應生成物,亦包含存在於化合物(2)中的2個 以上-COF基中僅1個被酯化之下述化合物(3-10)。化合 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) _ 14 . 584628 經濟部智慧財產局員工消費合作社印製 A7 ____B7 _五、發明説明(12 ) 物(3-1〇)中的R1、R2、Qf& n與上述同義。 Qf ( -COF) ^ ( -COOCHRiR2) · ·•式(3-10) 此化合物(3-10)的生成量增多表示此非有效率的製 造方法,故對酯化反應生成物的全量之化合物(3)量超過 5〇莫耳%爲佳,超過60莫耳%爲特佳。 酯化反應的生成物,可依其目的而進行純化,或使用 下述反應等亦可,由欲使下步驟之氟化反應能順利進行的 觀點來看,進行純化較爲佳。特別爲酯化反應生成物含有 化合物(1 )時,經純化將化合物(1 )除去較佳。 作爲純化方法,可舉出以水等處理生成物後進行分餾 之方法、以適當的有機溶劑萃取後進行蒸餾的方法、二氧 化矽膠體管柱層析法等。 本發明中,將酯化反應生成物進行酯化。氟化反應如 後述以液相氟化反應實施較佳。欲能順利進行液相氟化反 應,酯化反應生成物(特別爲化合物(3 ))的平均氟含量 爲20〜60質量%爲佳,以25〜55質量%爲特佳,30〜55 質量%爲最佳。對於酯化反應生成物而言,平均氟含量欲 能至該範圍而調節化合物(2 )的Qf構造及碳數爲佳。又 ,酯化反應生成物的分子量以200〜1100範圍爲佳,特別 爲300〜800範圍爲佳。平均氟含量對於特定範圍內的酯化 反應生成物而言,會大大提高氟化反應時液相中之溶解性 ,有著提升液相氟化反應的操作性、反應收率之優點,又 平均氟含量於特定範圍內,亦有著較佳經濟性之優點。若 酯化反應生成物的分子量爲特定分子量以上時,有著迴避 本紙張尺度適用中國國家標準(CNS ) A4規格(210 X297公釐) _ _ (請先閲讀背面之注意事項再填寫本頁) 584628 A7 _B7_ 五、發明説明(13 ) 氣相氟化反應引起分解反應之優點,該分子量於特定量以 下時,有著化合物較易處理或生成物較易純化之優點。 氟化反應可使用氟化鈷的氟化法、電化學的氟化法、 或與氟(elemental fluorine)進行反應之方法等實施。其中 ,可不顧基質的構造而有效率地實施反應,及氟化反應的 收率格外高等理由來看,液相中與氟反應的之液相氟化法 爲佳。以下舉出液相氟化法例子說明氟化反應。 作爲液相氟化法的液相,既使爲反應基質本身亦可, 但一般以與生成物或反應無關的氟化反應溶劑爲佳。氟可 直接使用,或使用以惰性氣體稀釋的氟氣爲佳。作爲惰性 氣體以氮氣、氨氣爲佳,由經濟上的理由來看以氮氣爲特 佳。氮氣中的氟氣量並無特別限定,以lOvol%以上時因效 率高故佳,特別以20vol%以上爲特佳。 作爲氟化反應溶劑,氟化反應中以惰性溶劑爲佳,且 以使用酯化反應生成物之溶解性較高的溶劑爲特佳。特別 爲可溶解1質量%以上的酯化反應生成物之溶劑,特別爲 可溶解5質量%以上的溶劑爲佳。 作爲氟化反應溶劑的例子,化合物(2 )、後述化合物 (4)、含氟羰基化合物(5)、全氟鏈烷類(商品名:FC-72等)、全氟醚類(商品名:FC-7 5、FC-77等)、全氟聚 酯類(商品名:clitox、fanbulin、galden、demnam 等)、 氯氟碳類(商品名:fronrub )、氯氟聚醚類、全氟烷基胺 (例如,全氟三烷基胺等)、惰性流體(商品名:flornate )等。其中化合物(2)或含氟羰基化合物(5)作爲氟化 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) _ 16 _ (請先閱讀背面之注意事項再填寫本頁) -裝- 訂(Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The manufacturing method of the present invention is to perform esterification reaction, fluorination reaction, and decomposition reaction of ester bonds. For the starting compound (1), the method of the present invention is a method which is advantageous when the molecular weight of the compound (1) is small. Therefore, the carbon number of the RtHR2- part is preferably 3 to 10, particularly preferably 3 to 5. . The molecular weight of the compound (1) is preferably 32 to 200, particularly preferably 60 to 150, and most preferably 60 to 120. In the compound (1), when R1 and R2 are fluorinated monovalent organic groups, an alkyl group, an epoxy group, and an alkoxy group are preferred. When R1 and R2 are simultaneously fluorinated to form a divalent organic group, as the divalent organic group, a group having one or more ethereal oxygen atoms interposed between the alkylene group or the carbon-carbon bond of the alkylene group. Better. In addition, as the compound (1), alcohol compounds having various structures can be purchased at low cost, so those having no winning atoms (that is, compounds having a fluorine content of 0% by mass) are preferred. As the compound (1), a compound having a structure corresponding to the intended fluorine-containing ore-based compound (5) is selected and used. Compound R1 in compound (1) or this paper is applicable in g | National Standard (CNS) A4 specification (2 丨 〇 > < 297 mm) -11-584628 A7 _____B7_ V. Description of the invention (9) (please first Read the notes on the back and fill in this page again.) The arrangement of the R2 carbon skeleton is maintained by the Rlf & rule of the fluorine-containing carbonyl compound (5). When the fluorine-containing carbonyl compound (5) is used as the raw material of the fluorine-containing primary alcohol The compound (1) using R2 as a hydrogen atom is preferred. When the fluorine-containing carbonyl compound (5) is used as a raw material of the fluorine-containing secondary alcohol, the compound (1) using R2 as a fluorinated monovalent organic group is In the present invention, the compound (1) is subjected to an esterification reaction with the compound (2). The compound (2) means that at the bond point of the perfluorinated η-valent organic group (Qf), η- A compound of a group represented by COF. Η represents an integer of 2 or more. Qf represents a perfluorinated η-valent saturated hydrocarbon group or a perfluorinated group (an η-valent saturated hydrocarbon group containing an etheric oxygen atom) is preferred. This group (Qf When) is a divalent group (Qf2), a perfluoroalkylene group or a perfluoro (alkylene group containing an etheric oxygen atom) group is particularly preferred. As the compound (2), it is better because FC0 (CF2) kC〇F (k represents an integer of 2 to 8) is easier to obtain, and the reaction yield is high. The present invention is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs For the production method, the compound (2) can be subjected to a stoichiometric method to obtain n-fold mole fluorocarbonyl compound (5). The compound (2) can be recovered, and the recovered compound (2) can be recovered. Can be used multiple times. The method used to recover compound (2) is described later. Specific examples of compound (2) include compound (2-1) when η is 2 described later. Compound (1) and compound (2) The reaction of) can be carried out under well-known esterification reaction conditions. The esterification reaction can be carried out in the presence of an esterification reaction solvent, but it is better from the viewpoint of volumetric efficiency when carried out in the absence of an esterification reaction solvent. When using an esterification reaction solvent, dichloromethane, chloroform, triethylamine, and this paper are applicable. National National Standard (CNS) A4 Specification (210X297 mm) -12-584628 A7 _ B7_ V. Description of the Invention ( 10) (Please read the notes on the back first (Write this page) or a mixed solvent of triethylamine and tetrahydrofuran. The amount of the esterification reaction solvent is preferably 50 to 5000% by mass based on the total amount of the compound (1) and the compound (2). In the reaction between the compound (1) and the compound (2), fluoric acid (HF) is generated, and alkali metal fluorides (preferably NaF and KF) or trialkylamines can exist in the reaction system as HF trapping agents. HF scavenger is preferably used when the reaction-related compound is an acid-labile compound. When HF scavenger is not used, the reaction is carried out at a reaction temperature at which gaseable HF can be generated, and HF and nitrogen are simultaneously discharged from the reaction system. Outside is better. The amount of the HF trapping agent is preferably about 1 to 10 times the molar amount for the theoretical generation of HF. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This esterification reaction is an esterification reaction of a bifunctional acid fluoride or more and a monofunctional alcohol. In this esterification reaction, when the reaction between a highly polar difunctional alcohol or more and a monofunctional acid fluoride is compared, the reaction speed and the reaction result are also high. Further, the alcohol remaining in the product after the esterification reaction is not preferable as described below. From the above, it is understood that the amount of the compound (1) used in the esterification reaction is preferably equal to or less than η Mor (η is the number of bases (η) represented by -COF in the corresponding compound (2)) for the compound (2). It is not economical to use the compound (1) exceeding η, and unreacted compound (1) remains in the reaction product of the esterification reaction. When the unreacted compound (1) remains in the esterification reaction product, a reaction that is not good for the fluorination reaction is caused. Therefore, the amount of the compound (1) used in the esterification reaction is preferably an amount that does not remain in the esterification reaction product, and purification of the esterification reaction product may be omitted. In particular, the amount of the compound (1) is particularly preferably from 0.5η times to η times mole, and most preferably 0.9η times to η times mole. This paper size is applicable. National National Standard (CNS) A4 specification (210 × 297 mm) 771 ~ 584628 A7 B7 V. Description of the invention (11) The advantages of the invention using compound (2), especially the compound (1) Play when molecular weight is relatively low. Since the compound (2) has a fluorenyl fluoride group on the structure (please read the notes on the back before filling this page), more than two compounds (1) in the compound (2) will react. As a result, compared with the case where the compound (1) is reacted in a compound having one fluorenyl fluoride group, since the molecular weight of the compound (3) is larger and the vapor pressure is smaller, it is easier to control the liquid phase fluorination. The reaction proceeds in a reaction with a high yield and is also advantageous for volume efficiency. The lower limit of the reaction temperature of the esterification reaction is generally -50 ° C, the upper limit is + 100 ° C, and the boiling point of the esterification solvent is preferably lower. In addition, the reaction reaction time is appropriately changed in accordance with the feed rate of the raw materials and the amount of the compound actually reacted. The reaction pressure is preferably normal pressure to 2 MPa (gauge pressure, and the following pressure indicates the gauge pressure). The product of the esterification reaction printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs must contain more than one compound (3). R ^ RlQf and η in the compound (3) have the same meanings as described above. m represents the number of radicals (-COOCHW) formed by the esterification reaction, and is an integer of 2 or more and η or less. (N-m) represents the number of -COF groups left without being esterified. When (n-m) is 0, it means that the -COF group of the compound (2) does not exist. Examples of the compound (3) include compounds in which (nm) is 0, compounds in which n > m (that is, compounds in which at least two -COF groups of compound (2) are esterified, but not all esterified compounds ), These ratios are not particularly limited. The esterification reaction product of the present invention, that is, all products produced by the esterification reaction, also contains compounds other than the compound (3). For example, the esterification reaction product also includes the compound (2). Of the two or more -COF groups, only one of the following compounds (3-10) is esterified. The size of the composite paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) _ 14. 584628 Printed by A7 ____B7 _ in the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (12) in the product (3-1〇) R1, R2, Qf & n are synonymous with the above. Qf (-COF) ^ (-COOCHRiR2) ···· Formula (3-10) The increase in the amount of production of this compound (3-10) indicates this inefficient production method, so it is a compound for the entire amount of the esterification reaction product (3) An amount exceeding 50 mol% is preferred, and an amount exceeding 60 mol% is particularly preferred. The product of the esterification reaction may be purified depending on its purpose, or the following reactions may be used. From the viewpoint of smoothing the fluorination reaction in the next step, it is preferable to purify the product. In particular, when the esterification reaction product contains the compound (1), the compound (1) is preferably removed by purification. Examples of the purification method include a method in which the product is treated with water and then fractionated, a method in which extraction is performed with an appropriate organic solvent and then distilled, and silica gel column chromatography. In the present invention, the esterification reaction product is esterified. The fluorination reaction is preferably carried out as a liquid phase fluorination reaction as described later. For a smooth liquid phase fluorination reaction, the average fluorine content of the esterification reaction product (especially the compound (3)) is preferably 20 to 60% by mass, particularly 25 to 55% by mass, and 30 to 55% by mass. % Is best. For the esterification reaction product, it is preferable to adjust the Qf structure and carbon number of the compound (2) so that the average fluorine content is within this range. The molecular weight of the esterification reaction product is preferably in the range of 200 to 1100, and particularly preferably in the range of 300 to 800. The average fluorine content for the esterification reaction products in a specific range will greatly improve the solubility in the liquid phase during the fluorination reaction, and has the advantages of improving the operability and reaction yield of the liquid phase fluorination reaction. If the content is in a specific range, it also has the advantage of better economy. If the molecular weight of the esterification reaction product is above a certain molecular weight, there is a circumvention of the Chinese national standard (CNS) A4 specification (210 X297 mm) for this paper size. _ _ (Please read the precautions on the back before filling this page) 584628 A7 _B7_ V. Description of the invention (13) The gas phase fluorination reaction has the advantage of decomposition reaction. When the molecular weight is below a certain amount, it has the advantage that the compound is easier to handle or the product is easier to purify. The fluorination reaction can be carried out using a fluorination method of cobalt fluoride, an electrochemical fluorination method, or a method of reacting with elemental fluorine. Among them, the liquid phase fluorination method which reacts with fluorine in the liquid phase is preferable because the reaction can be carried out efficiently regardless of the structure of the substrate, and the yield of the fluorination reaction is particularly high. An example of a liquid phase fluorination method is given below to illustrate the fluorination reaction. The liquid phase of the liquid phase fluorination method may be a reaction substrate itself, but a fluorination reaction solvent that is not related to a product or a reaction is generally preferred. Fluorine can be used directly, or fluorine gas diluted with an inert gas is preferred. As the inert gas, nitrogen and ammonia are preferable, and for economic reasons, nitrogen is particularly preferable. The amount of fluorine in the nitrogen gas is not particularly limited, and it is preferably at 10 vol% or more because of its high efficiency, and particularly preferably at 20 vol% or more. As the fluorination reaction solvent, an inert solvent is preferred in the fluorination reaction, and a solvent having a higher solubility using an esterification reaction product is particularly preferred. Particularly, it is a solvent capable of dissolving 1% by mass or more of the esterification reaction product, and particularly preferably a solvent capable of dissolving 5% by mass or more of the solvent. Examples of the fluorination reaction solvent include compound (2), compound (4) described later, fluorine-containing carbonyl compound (5), perfluoroalkanes (trade name: FC-72, etc.), and perfluoroethers (trade name: FC-7 5, FC-77, etc.), perfluoropolyesters (brand names: clitox, fanbulin, galden, demnam, etc.), chlorofluorocarbons (brand name: fronrub), chlorofluoropolyethers, perfluoroalkanes Amines (for example, perfluorotrialkylamines, etc.), inert fluids (trade name: flornate), and the like. Among them, compound (2) or fluorine-containing carbonyl compound (5) is fluorinated. The paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) _ 16 _ (Please read the precautions on the back before filling this page)- Pack-order
經濟部智慧財產局員工消費合作社印製 W 584628 A7 B7 五、發明説明(14 ) (請先閲讀背面之注意事項再填寫本頁) 反應溶劑使用時,因有後處理較容易的優點而佳。氟化反 應溶劑的量,對酯化反應生成物的總質量而言,以5倍質 量以上爲佳,特別爲10〜IX 1〇5倍質量爲佳。 氟化反應的反應形式,可使用分批方式或連續方式皆 可。例如,可舉出反應器中裝入氟化反應溶劑與酯化反應 生成物,經攪拌再將氟氣連續供給於氟化反應溶劑中使其 反應的方法。又,可舉出反應器中裝入氟化反應溶劑經攪 拌,再將氟氣與酯化反應生成物以所定的莫耳比連續供給 於氟化反應溶劑中之方法。其中,氟化反應由反應收率與 選擇率的觀點來看,實施後者較佳。又,該方法中氟氣以 氮氣等惰性氣體稀釋後使用爲佳。 使用於氟化反應的氟,對於含於酯化反應生成物中的 氫原子量之氟量,於反應最初至最後保持過剩當量狀態爲 佳,特別保持對氫原子的氟量以1.05倍當量以上(及1.05 倍莫耳以上)時的由選擇率的觀點看較佳。又,欲將氟量 於反應起始點開始即呈過剩狀態,使用於反應當初的氟化 反應溶劑中,預先溶解充分量的氟爲佳。 經濟部智慧財產局員工消費合作社印製 又,氟化反應因必須於未切斷化合物(3 )中的酯鍵下 實施,故反應溫度的下限以酯化反應生成物之沸點中最低 溫爲佳。一般狀況下,由反應收率、選擇率、及工業上較 易實施的觀點來看,反應溫度以-5 0°C〜+ 100 °C爲特佳, -20 °C〜+ 50°C爲最佳。氟化反應的反應壓力雖無特別限定 ,但以常壓〜2MPa時由反應收率、選擇率、工業上較易實 施的觀點看特佳。 -17- 巧3本紙張尺度適用中.國國家標準(€奶)八4規格(210父297公釐) 584628 A7 B7 五、發明説明(15 ) (請先閱讀背面之注意事項再填寫本頁) 且,欲有效率地進行氟化反應,反應系統中添加含C-H鍵結化合物,長時間將酯化反應生成物滯留於反應系統 內,或進行紫外光照射等操作爲佳。這些操作以氟化反應 的後期進行較佳。又,化合物(3 )的R2表示氫原子以外 的基時,R2及R1所鍵結的碳原子中所鍵結的氫原子可較易 氟化,故進行該操作爲佳。這些操作可將存在於反應系統 的酯化反應生成物有效率地氟化,反應率可大大提高。 作爲含有C-H鍵結的化合物,以芳香族烴爲佳,即以 苯、甲苯等爲佳。該含有C-H鍵結的化合物之添加量,對 酯化反應生成物中的氫原子總量而言以0.1〜1 0莫耳%爲佳 ,特別以0.1〜5莫耳%爲特佳。含有C-H鍵結的化合物, 添加於存在氟的反應系統中爲佳。又,添加含有C-H鍵結 的化合物時,加壓反應系統爲佳。加壓時以〇.〇 Γ〜5MPa爲 佳。又,進行紫外線照射時以0.1〜3小時照射爲佳。 氟化反應中,酯化反應生成物經全氟化後,生成含有1 種以上的化合物(4)之氟化反應生成物。化合物(4)爲 化合物(3 )經全氟化之化合物。 經濟部智慧財產局員工消費合作社印製 本發明的氟化反應生成物,含有酯化反應生成物經氟 化之所有生成物,但必須有化合物(4 )。氟化反應生成物 的組成依酯化反應生成物的組成而改變,含有2種以上的 酯化反應生成物之化合物時,氟化反應生成物亦爲2種以 上。 化合物(4 )中,Qf、η及m爲對應化合物(3 )。化合 物(4)的Rlf爲經全氟化後之1價有機基時,以全氟烷基 張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 一 584628 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明(16 ) 、全氟環院基、全贏焼氧基等爲佳,其中以全氟院基爲最 佳。爲經全氟化後之1價有機基時,以全氟烷基爲最佳 。又,作爲义〃與R2f—起形成該2價被全氟化之基時的該 全氟化基,全氟化2價飽和烴基或全氟(含有醚性氧原子 的2價飽和烴)基爲佳,全氟伸烷基、或伸烷基的碳-碳鍵 結間插入1以上的醚性氧原子之基經全氟化之基爲特佳。 酯化反應生成物含有化合物(3-10)時,該化合物亦 含於經全氟化的下述化合物(4-10)或氟化反應生成物中 。化合物(4-10)的η、Qf、R2f、Rlf爲對應化合物(3-10 )° QfGCOFh-K-COOCFRURH).·.式(4-10) 且,氟化反應生成物中酯化反應生成物含於1種以上 的部分氟化之化合物(以下這些部分氟化合物亦稱爲氫素 殘留化合物)。 液相中氟化中會副產生氫原子經氟原子取代之HF。欲 除去HF,反應系中共存HF捕捉劑,於反應器氣體出口將 HF捕捉劑與出口氣體接觸,或冷卻出口氣體將HF凝集回 收爲佳。作爲該HF捕捉劑可使用如上述相同者,以NaF爲 佳。又,氮氣等情性氣體同時與HF導出反應系統外,以鹼 處理較佳。 反應系統中共存HF捕捉劑時的量,對於酯化反應生成 物中所存在的全氫原子量而言,爲1〜20倍莫耳爲佳,1〜 5倍莫耳爲特佳。反應器出口放置HF捕捉劑時,(a )冷卻 器(10°C〜室溫,特別爲保持約2(TC爲佳)(b) NaF小球 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中.國國家標準(CNS ) A4規格(210X297公釐) -19- 584628 A7 B7 五、發明説明(17 ) (請先閱讀背面之注意事項再填寫本頁) 塡充層、及(C)冷卻器(-7 8°c〜+ lot:,特別爲保持-3 0 °C〜〇 °C爲佳)以(a ) - ( b ) - ( c )的順序直列設置爲佳。 又,欲由(c )的冷卻器凝集的液體回到反應器,可設置液 體回送路線。 氟化反應生成物可直接使用於下個步驟,可經純化而 成爲高純度者。作爲純化方法,可舉出將粗生成物直接於 常壓或減壓下蒸餾之方法等。 本發明中,更進行對氟化反應生成物的酯鍵分解反應 。酯鍵的分解反應,係爲可切斷化合物中所存在的酯鍵, 形成化合物(2)與含氟羰基化合物(5)之反應,其爲公 知反應。酯鍵的分解反應,係於熱分解反應或親核劑或親 電子劑的存在下進行分解反應較佳。 熱分解反應可經加熱氟化反應生成物而實施。作爲熱 分解反應的反應形式,由氟化反應生成物之沸點與其安定 性而做選擇爲佳。 經濟部智慧財產局員工消費合作社印製 例如,對於沸點較低的氟化反應生成物進行熱分解反 應時,採用氣相熱分解法爲佳。氣相熱分解法係於氣相下 連續進行分解反應,所生成的含氟羰基化合物(5 )與化合 物(2 )由出口氣體使其凝縮,將此回收的方法下進行爲佳 〇 氣相熱分解法的反應溫度以5 0〜3 5 0 °C爲佳,5 0〜3 0 0 °C爲特佳,而1 5 0〜2 5 0 °C爲最佳。氣相熱分解法中,可使 用金屬鹽觸媒,或反應系統中共存與反應無直接關連之惰 性氣體亦可。作爲惰性氣體,可舉出氮氣、二氧化碳氣體 本紙張尺度適用中.國國家標準(CNS ) A4規格(210X:297公釐) :2〇 - 584628 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明(18 ) 等。惰性氣體的添加量,對氟化反應生成物的總量而言爲 0.01〜50vol%程度爲佳。若惰性氣體的添加量過多時,會 降低生成物的回收量。 另一方面,氟化反應生成物的沸點較高時,可採用反 應器內直接以液體的狀態加熱之液相熱分解法爲佳。未限 定液相熱分解法的反應壓力。該分解反應的生成物可由反 應器中一次取出亦可。又,利用與氟化反應生成物相比, 一般以酯鍵的分解反應生成物具有較低沸點之特點,使用 附蒸餾塔的反應裝置進行氟化反應,生成物一邊由蒸餾下 取出一邊進行反應亦可。液相熱分解法的反應溫度以50〜 3 00 °C爲佳。特別以100〜2501爲佳。 液相熱分解法,可於無溶劑下進行或分解反應溶劑存 在下進行亦可,但以無溶劑下進行爲佳。使用分解反應溶 劑時,使用於反應中呈現惰性之溶劑,且與氟化反應生成 物具有相溶性者爲佳。又,分解反應溶劑可使用較易由生 成物分離者。作爲分解反應溶劑的具體例子,以全氟化三 烷基胺、全氟化萘等惰性溶劑、高沸點氯氟碳之氯三氟乙 儲寡聚物(例如商品名:福龍路普)爲佳。又,分解反應 溶劑的量,對氟化反應生成物而言爲0. 1 0倍〜1 0倍質量爲 佳。 液相中與親核劑或親電子劑反應進行酯鍵的分解反應 時,可於無溶劑下進行或分解反應溶劑存在下進行亦可, 但以無溶劑下進行爲佳。所謂無溶劑下進行反應,氟化反 應生成物本身亦可作爲溶劑而作用,因可省略反應生成物 本紙張尺度適用中.國國家標準(CNS〉A4規格(210X297公釐)^91 . (請先閲讀背面之注意事項再填寫本耳) 584628 A7 ___ B7_ 五、發明説明(19 ) 中分離溶劑的步驟而特佳。使用親核劑或親電子劑的方法 ,亦可由附蒸餾塔的反應裝置下邊進行蒸餾邊進行爲佳。 (請先閲讀背面之注意事項再填寫本頁) 作爲親核劑以F·爲佳,特別來自鹼金屬的氟化物之F· 爲佳。作爲鹼金屬的氟化物,以NaF、NaHF2、KF、CsF爲 佳,由經濟的觀點來看以NaF,以反應活性的觀點來看以 KF爲特佳。又,反應的最初親核劑量可爲觸媒量,或亦可 爲過剩量。F·等親核劑的量對氟化反應生成物而言以1〜 500莫耳%爲佳,1〜100莫耳%爲特佳,而5〜50%爲最佳 。反應溫度的下限以-30 °C爲佳,上限以-20 °C〜250 °C爲特 佳。 本發明的分解反應生成物,含有由酯鍵分解反應所生 成的所有生成物,必須含有化合物(2 )與含氟羰基化合物 (5)。因化合物(4-10)的酯鍵分解反應所生成的化合物 亦爲化合物(2 )與含氟羰基化合物(5 ),故化合物(4-1 〇 )與化合物(4 )同時進行酯鍵的分解反應爲佳。作爲化 合物(2)與含氟羰基化合物(5)以外之分解反應生成物 ,可舉出如後述的殘留氫化合物的酯鍵經分解的化合物。 經濟部智慧財產局員工消費合作社印製 作爲本發明的含氟羰基化合物(5),爲R2f-COF或 Rlf-CO-R2f。本發明中,由分解反應生成物分別分離化合物 (2)與含氟羰基化合物(5)得到含氟羰基化合物(5)爲 佳。作爲分離方法以蒸餾法爲佳。 由本發明的方法得到的含氟羰基化合物(5 ),可直接 或變換成其他化合物而使用於種種用途之有用化合物。作 爲轉換爲其他化合物的例子,經熱分解反應於末端導入不 -22- 本紙張尺度適用中.國國家標準(CNS ) A4規格(210 X 297公釐) 584628 A7 _B7_ 五、發明説明(2〇 ) 飽和鍵結之使用於氟樹脂的單體例子、或經還原反應將末 端成爲羥基而製造氟醇的例子。 (請先閱讀背面之注意事項再填寫本頁) 且,含於分解反應生成物中的化合物(2 )的一部份或 全部,可作爲與化合物(1 )反應的化合物(2 )以可回收 利用者於製造上有利而佳。化合物(2 )由分解反應生成物 中回收再利用的方法,係爲化合物(1 )添加於反應系統中 ,連續製造含氟羰基化合物(5 )之方法。該連續製造方法 貫施1次循运時’化學量論上由1莫耳的化合物(2)可生 成η莫耳的含氟簾基化合物(5)與1莫耳的化合物(2) 〇 經濟部智慧財產局員工消費合作社印製 且,本發明的製造方法,η爲2的化合物因實施時反應 的控制或化合物(2 )的調節較容易故較佳,特別爲實施^ 爲2且Qf爲經全氟化之2價有機基(Qf2)之化合物(2-1) 爲佳。即,化合物(1 )與化合物(2-1 )經酯化反應得到含 有1種以上的化合物(3-1 )之酯化反應生成物,該酯化反 應生成物經氟化反應之全氟化後,得到含有1種以上的化 合物(心1 ),該氟化反應生成物中藉由進行酯鍵的分解反 應,可得到含有化合物(4-1 )與化合物(2-1 )的分解反應 生成物,由該分解反應生成物得到含氟羰基化合物(5 )作 爲特徵之含氟羰基化合物的製造方法爲佳。但,下式中的 R1、R2、1^”、1^及Qf2與上述意義相同。 FCOQf2COF.·····式(2-1) I^CHI^OCOQUCOOCHR1!^......式(3-1)Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs W 584628 A7 B7 V. Description of the invention (14) (Please read the precautions on the back before filling this page) When using the reaction solvent, it is better because it has the advantage of easier post-processing. The amount of the fluorination reaction solvent is preferably 5 times the mass or more, and more preferably 10 to IX 105 times the mass of the total mass of the esterification reaction product. The reaction form of the fluorination reaction may be a batch method or a continuous method. For example, a method in which a fluorination reaction solvent and an esterification reaction product are charged into a reactor, and a fluorine gas is continuously supplied to the fluorination reaction solvent to perform reaction while stirring. Another example is a method in which a fluorination reaction solvent is charged into the reactor and stirred, and then a fluorine gas and an esterification reaction product are continuously supplied to the fluorination reaction solvent at a predetermined molar ratio. Among them, the fluorination reaction is preferably carried out from the viewpoint of reaction yield and selectivity. In this method, the fluorine gas is preferably used after being diluted with an inert gas such as nitrogen. For the fluorine used in the fluorination reaction, the amount of fluorine contained in the hydrogenation product in the esterification reaction product is preferably maintained in an excess equivalent state from the beginning to the end of the reaction. In particular, the amount of fluorine to the hydrogen atom is 1.05 times the equivalent or more ( And 1.05 mol or more) from the viewpoint of selectivity. In addition, if the amount of fluorine is to be in an excess state from the start of the reaction, it is preferable to dissolve a sufficient amount of fluorine in advance in the fluorination reaction solvent used at the beginning of the reaction. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, because the fluorination reaction must be carried out under the ester bond in the compound (3) that is not cut off, so the lower limit of the reaction temperature is preferably the lowest temperature of the boiling point of the esterification reaction product. . In general, from the viewpoint of reaction yield, selectivity, and industrial ease of implementation, the reaction temperature is particularly preferably -50 ° C to + 100 ° C, and -20 ° C to + 50 ° C is optimal. Although the reaction pressure of the fluorination reaction is not particularly limited, it is particularly preferable from the standpoint of reaction yield, selectivity, and industrial ease of implementation at normal pressure to 2 MPa. -17- Qiao 3 paper sizes are applicable. National standard (€ milk) 8 4 specifications (210 father 297 mm) 584628 A7 B7 V. Description of the invention (15) (Please read the precautions on the back before filling this page In order to efficiently perform the fluorination reaction, it is preferable to add a CH-containing compound to the reaction system, and leave the esterification reaction product in the reaction system for a long time, or perform operations such as ultraviolet light irradiation. These operations are preferably performed at a later stage of the fluorination reaction. When R2 of the compound (3) represents a group other than a hydrogen atom, the hydrogen atom bonded to the carbon atom bonded to R2 and R1 can be easily fluorinated, so this operation is preferably performed. These operations can efficiently fluorinate the esterification reaction product existing in the reaction system, and the reaction rate can be greatly improved. The compound containing a C-H bond is preferably an aromatic hydrocarbon, that is, benzene, toluene, or the like. The addition amount of the C-H bond-containing compound is preferably 0.1 to 10 mole%, and particularly preferably 0.1 to 5 mole%, based on the total amount of hydrogen atoms in the esterification reaction product. The compound containing a C-H bond is preferably added to a reaction system in which fluorine is present. When a compound containing a C-H bond is added, a pressurized reaction system is preferred. When pressurizing, it is preferably from 0.00 to 5 MPa. In addition, it is preferable to irradiate ultraviolet rays for 0.1 to 3 hours. In the fluorination reaction, the esterification reaction product is perfluorinated to produce a fluorination reaction product containing one or more compounds (4). Compound (4) is a compound of compound (3) which has been perfluorinated. Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The fluorination reaction product of the present invention contains all products fluorinated from the esterification reaction product, but must have a compound (4). The composition of the fluorination reaction product varies depending on the composition of the esterification reaction product. When two or more compounds of the esterification reaction product are contained, the number of the fluorination reaction products is two or more. In compound (4), Qf, η, and m are corresponding compounds (3). When Rlf of compound (4) is a monovalent organic group after perfluorination, the Chinese National Standard (CNS) A4 specification (210X297 mm) is applied to the perfluoroalkyl sheet standard. 584628 A7 B7 Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Consumption cooperatives printed 5. Invention Description (16), perfluorinated bases, all-win fluorenyl radicals, etc., of which perfluorinated bases are the best. When it is a monovalent organic group after perfluorination, a perfluoroalkyl group is the best. Also, as the perfluorinated group when Y2 and R2f together form the divalent perfluorinated group, a perfluorinated divalent saturated hydrocarbon group or a perfluoro (divalent saturated hydrocarbon containing etheric oxygen atom) group Preferably, a perfluoroalkylene group, or a carbon-carbon bond of an alkylene group, in which a group having an etheric oxygen atom of 1 or more inserted through a perfluorinated group is particularly preferred. When the esterification reaction product contains the compound (3-10), the compound is also contained in the following compound (4-10) or the fluorination reaction product after perfluorination. Η, Qf, R2f, and Rlf of compound (4-10) are corresponding compounds (3-10) ° QfGCOFh-K-COOCFRURH) .. Formula (4-10) In addition, the esterification reaction in the fluorination reaction product produces The compound contains one or more partially fluorinated compounds (hereinafter these partially fluorinated compounds are also referred to as hydrogen residual compounds). Fluorine in the liquid phase will by-produce HF with hydrogen atoms replaced by fluorine atoms. To remove HF, it is better to co-exist HF trapping agent in the reaction system, contact the HF trapping agent with the outlet gas at the reactor gas outlet, or cool the outlet gas to agglomerate and recover HF. As the HF trapping agent, the same ones as described above can be used, and NaF is preferred. In addition, the sentimental gas such as nitrogen is taken out of the reaction system with HF at the same time, and alkali treatment is preferred. The amount of the HF scavenger coexisting in the reaction system is preferably 1 to 20 times the mole and particularly preferably 1 to 5 times the mole of the total hydrogen atoms present in the esterification reaction product. When placing HF trapping agent at the reactor outlet, (a) cooler (10 ° C ~ room temperature, especially to maintain about 2 (TC is preferred)) (b) NaF pellet (please read the precautions on the back before filling this page) ) This paper size is applicable. National National Standard (CNS) A4 specification (210X297 mm) -19- 584628 A7 B7 V. Description of invention (17) (Please read the precautions on the back before filling this page) 塡And (C) cooler (-7 8 ° c ~ + lot :, especially to maintain -3 0 ° C ~ 0 ° C) is best set in the order of (a)-(b)-(c) In addition, the liquid to be condensed from the cooler of (c) can be returned to the reactor, and a liquid return route can be set. The fluorination reaction product can be used directly in the next step, and can be purified to become high purity. As a purification method Examples include a method of directly distilling the crude product under normal pressure or reduced pressure. In the present invention, an ester bond decomposition reaction is further performed on the fluorination reaction product. The ester bond decomposition reaction is cleavable. The ester bond present in the compound forms the reaction between compound (2) and fluorine-containing carbonyl compound (5), which is a well-known reaction The ester bond decomposition reaction is preferably performed in the presence of a thermal decomposition reaction or a nucleophile or an electrophile. The thermal decomposition reaction can be carried out by heating the fluorinated reaction product. As a reaction form of the thermal decomposition reaction It is better to choose based on the boiling point of the fluorinated reaction product and its stability. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. For example, for the thermal decomposition reaction of a fluorinated reaction product with a lower boiling point, gas phase heat is used. The decomposition method is preferred. The gas phase thermal decomposition method continuously performs the decomposition reaction in the gas phase, and the generated fluorine-containing carbonyl compound (5) and the compound (2) are condensed by an outlet gas, and the recovery method is performed as follows. The reaction temperature of the gas phase thermal decomposition method is preferably 50 to 350 ° C, 50 to 300 ° C is particularly preferable, and 150 to 250 ° C is the best. Gas phase In the thermal decomposition method, a metal salt catalyst may be used, or an inert gas coexisting in the reaction system that is not directly related to the reaction may be used. Examples of the inert gas include nitrogen gas and carbon dioxide gas. This paper is applicable to this paper. National Standard (CNS ) A4 Regulation (210X: 297 mm): 20-584628 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 5. Invention Description (18), etc. The amount of inert gas added is relative to the total amount of fluorinated reaction products It is preferably about 0.01 to 50 vol%. If the amount of the inert gas added is too large, the recovery amount of the product will be reduced. On the other hand, when the boiling point of the fluorination reaction product is high, the liquid in the reactor can be used directly. The liquid-phase thermal decomposition method with a state heating is preferable. The reaction pressure of the liquid-phase thermal decomposition method is not limited. The product of the decomposition reaction may be taken out from the reactor at one time. In addition, compared with the fluorinated reaction product, the decomposition reaction product with an ester bond generally has a lower boiling point. The fluorination reaction is performed using a reaction device with a distillation column, and the product is reacted while being taken out from the distillation. Yes. The reaction temperature of the liquid thermal decomposition method is preferably 50 to 300 ° C. Particularly preferred is 100 to 2501. The liquid-phase thermal decomposition method may be carried out in the absence of a solvent or the decomposition reaction may be carried out in the presence of a solvent, but is preferably carried out in the absence of a solvent. When a decomposition reaction solvent is used, it is preferable to use a solvent that is inert during the reaction and is compatible with the fluorinated reaction product. The decomposition reaction solvent may be one which can be easily separated from the product. As specific examples of the decomposition reaction solvent, an inert solvent such as perfluorinated trialkylamine and perfluorinated naphthalene, and a high-boiling point chlorofluorocarbon chlorotrifluoroethane storage oligomer (for example, trade name: Fulong Lupu) are good. Moreover, the amount of the decomposition reaction solvent is preferably 0.1 to 10 times by mass for the fluorination reaction product. When the ester bond is decomposed by reacting with a nucleophile or an electrophile in the liquid phase, it may be carried out in the absence of a solvent or in the presence of a decomposition reaction solvent, but it is preferably carried out without a solvent. The so-called reaction without solvent, the fluorinated reaction product itself can also function as a solvent, because the reaction product can be omitted. The paper size is applicable. National National Standards (CNS> A4 specifications (210X297 mm) ^ 91. (Please First read the notes on the back before filling in this ear) 584628 A7 ___ B7_ V. The step of separating the solvent in the description of invention (19) is particularly good. The method using nucleophile or electrophile can also be used by the reaction device with distillation tower It is better to perform the distillation below. (Please read the precautions on the back before filling out this page.) F · is preferred as the nucleophile, especially F · from the fluoride of alkali metals. It is the fluoride of alkali metals. NaF, NaHF2, KF, CsF is preferred, NaF is particularly preferred from an economic standpoint, and KF is particularly preferred from a reactive standpoint. In addition, the initial nucleophilic dose of the reaction may be the amount of catalyst, or It may be an excess amount. The amount of nucleophile such as F · is preferably 1 to 500 mole%, particularly preferably 1 to 100 mole%, and 5 to 50% is most preferable for the fluorination reaction product. The lower limit of the reaction temperature is preferably -30 ° C, and the upper limit is -20 ° C ~ 250 ° C. The product of the decomposition reaction of the present invention contains all the products produced by the ester bond decomposition reaction, and must contain the compound (2) and the fluorine-containing carbonyl compound (5). Because of the ester bond decomposition reaction of the compound (4-10) The resulting compound is also a compound (2) and a fluorine-containing carbonyl compound (5), so that the compound (4-1 〇) and the compound (4) are simultaneously subjected to an ester bond decomposition reaction. As the compound (2) and fluorine-containing compound Examples of the decomposition reaction products other than the carbonyl compound (5) include compounds in which the ester bond of the remaining hydrogen compound is decomposed as described later. The fluorocarbonyl compound (5) produced by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is produced by the present invention. Is R2f-COF or Rlf-CO-R2f. In the present invention, it is preferable to separate the compound (2) and the fluorine-containing carbonyl compound (5) from the decomposition reaction product to obtain the fluorine-containing carbonyl compound (5). As a separation method, Distillation is preferred. The fluorine-containing carbonyl compound (5) obtained by the method of the present invention can be used directly or indirectly as other compounds and useful compounds for various applications. Examples of conversion to other compounds It is not introduced at the end after thermal decomposition reaction -22- This paper size is applicable. National National Standard (CNS) A4 size (210 X 297 mm) 584628 A7 _B7_ V. Description of the invention (2) Saturation bonding is used in An example of a fluororesin monomer or an example of a fluoroalcohol produced by reducing the terminal to a hydroxyl group through a reduction reaction. (Please read the precautions on the back before filling out this page.) Also, the compound (2) contained in the decomposition reaction product A part or all of the compounds (2) which can be reacted with the compound (1) are advantageous and can be manufactured with good recyclability. The method for recovering and reusing the compound (2) from the decomposition reaction product is a method of continuously adding the compound (1) to the reaction system to produce a fluorocarbonyl compound (5). This continuous manufacturing method is performed once per cycle. 'Stoichiometrically, from 1 mole of compound (2), η mole of fluorine-containing curtain compound (5) and 1 mole of compound (2) can be produced. Printed by the Consumer Cooperative of the Ministry of Intellectual Property Bureau and the manufacturing method of the present invention, the compound with η of 2 is better because it is easier to control the reaction during the implementation or the adjustment of compound (2), especially for the implementation of ^ 2 and Qf is The compound (2-1) having a perfluorinated divalent organic group (Qf2) is preferred. That is, the esterification reaction of the compound (1) and the compound (2-1) yields an esterification reaction product containing one or more compounds (3-1), and the esterification reaction product is perfluorinated by a fluorination reaction. Then, one or more compounds (Heart 1) are obtained, and the decomposition reaction of the ester bond in the fluorination reaction product can be obtained by the decomposition reaction of the compound (4-1) and the compound (2-1). It is preferable to produce a fluorine-containing carbonyl compound (5) as a characteristic from the decomposition reaction product. However, R1, R2, 1 ^ ", 1 ^, and Qf2 in the following formulas have the same meaning as above. FCOQf2COF .............. Formula (2-1) I ^ CHI ^ OCOQUCOOCHR1! ^ ...... Formula (3-1)
RlfCFR2f〇C〇Qf2C〇〇CFRlfR2f…式(4-1) 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) _ 23 _ 584628 A7 B7 五、發明説明(21 ) 作爲本發明的化合物(1 )之具體例子,可舉出下述化 合物。 (CH3)2CHOH、RlfCFR2f〇C〇Qf2C〇CFRlfR2f ... Formula (4-1) This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) _ 23 _ 584628 A7 B7 V. Description of the invention (21) As the compound of the present invention Specific examples of (1) include the following compounds. (CH3) 2CHOH,
CyCH2OH(Cy表示環烷基。以下相同。)、CyCH2OH (Cy represents a cycloalkyl group. The same applies hereinafter).
CyOH、 CH2C1CHC1CH2CH20H、 (CH3)2CHCH2OH、 CH3CH2CH2OH。 作爲化合物(2)的具體例,可舉出下記化合物。 FCOCF2CF2COF、 FCOCF2CF2CF2CF2COF ' FCOCF(CF3)OCF2CF2CF2COF、 FCOCF(CF3)OCF2CF2CF2CF2COF、 FCOCF2CF(CF3)OCF2CF2CF2CF2COF、 FCOCF2CF(CF3)OCF2CF2CF2CF2CF2COF。 作爲化合物(3)的具體例,可舉出下記化合物。 (CH3)2CHOCOCF2CF2CF2CF2COOCH(CH3)2、 CyCH2OCOCF2CF2CF2CF2COOCH2Cy、 CyOCOCF2CF2CF2CF2COOCy、 CH2CICHCICH2CH2OCOCF2CF2CF2CF2COOCH2CH2CHC 1CH2C1、 (CH3)2CHCH2OCOCF2CF2CF2CF2COOCH2CH(CH3)2、 CH3CH2CH2OCOCF2CF2CF2CF2COOCH2CH2CH3。 作爲化合物(3-10)的具體例,可舉出下記化合物。 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) (請先閱讀背面之注意事項再填寫本頁) 裝' 、-!· 經濟部智慧財產局員工消費合作社印製 -24- 584628 A7 _B7__ 五、發明説明(22 ) (請先閲讀背面之注意事項再填寫本頁) (CH3)2CHOCOCF2CF2CF2CF2COF、 CyCH2OCOCF2CF2CF2CF2COF、 CyOCOCF2CF2CF2CF2COF、 CH2CICHCICH2CH2OCOCF2CF2CF2CF2COF ^ (CH3)2CHCH2OCOCF2CF2CF2CF2COF、 CH3CH2CH2OCOCF2CF2CF2CF2COF。 作爲化合物(4)的具體例,可舉出下記化合物。 (CF3)2CFOCO(CF2)4COOCF(CF3)2、CyOH, CH2C1CHC1CH2CH20H, (CH3) 2CHCH2OH, CH3CH2CH2OH. Specific examples of the compound (2) include the following compounds. FCOCF2CF2COF, FCOCF2CF2CF2CF2COF 'FCOCF (CF3) OCF2CF2CF2COF, FCOCF (CF3) OCF2CF2CF2CF2COF, FCOCF2CF (CF3) OCF2CF2CF2CF2COF, FCOCF2CF (CF3) OCF2CF2CF2CF2CF2CF2CF2CFF. Specific examples of the compound (3) include the following compounds. (CH3) 2CHOCOCF2CF2CF2CF2COOCH (CH3) 2, CyCH2OCOCF2CF2CF2CF2COOCH2Cy, CyOCOCF2CF2CF2CF2CF2COOCy, CH2CICHCICH2CH2OCOCF2CF2CF2CF2CF2CO2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2O2 Specific examples of the compound (3-10) include the following compounds. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling out this page). A7 _B7__ 5. Description of the invention (22) (Please read the precautions on the back before filling in this page) (CH3) 2CHOCOCF2CF2CF2CF2COF, CyCH2OCOCF2CF2CF2CF2COF, CyOCOCF2CF2CF2CF2CF2CF2CF2CF2CO2CO2CO2CO2CICH2CH2OCOCF2CF2CF2CF2CF2CF2CO2CO2COF2 Specific examples of the compound (4) include the following compounds. (CF3) 2CFOCO (CF2) 4COOCF (CF3) 2
CyfCF2OCO(CF2)4COOCF2Cyf(惟、Cy 表示過氟化環烷 基。以下相同。)、CyfCF2OCO (CF2) 4COOCF2Cyf (However, Cy represents a perfluorinated cycloalkyl group. The same applies below.),
CyfOCOCF2CF2CF2CF2COOCyf、 CF2CICFCICF2CF2OCOCF2CF2CF2CF2COOCF2CF2CFCIC F2CI ' (CF3)2CFCF2OCOCF2CF2CF2CF2COOCF2CF(CF3)2、 CF3CF2CF2OCOCF2CF2CF2CF2COOCF2CF2CF3 〇 作爲化合物(4-10)的具體例,可舉出下記化合物。 (CF3)2CFOCO(CF2)4COF、 經濟部智慧財產局員工消費合作社印製CyfOCOCF2CF2CF2CF2CF2COOCyf, CF2CICFCICF2CF2OCOCF2CF2CF2CF2COOCF2CF2CFCIC F2CI '(CF3) 2CFCF2OCOCF2CF2CF2CF2COOCF2CF (CF3) 2, CF3CF2CF2OCOCF2CF2CF2CF2CF2CF2CF2CFOCF. (CF3) 2CFOCO (CF2) 4COF Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs
CyfCF2OCO(CF2)4COF、CyfCF2OCO (CF2) 4COF,
CyfOCOCF2CF2CF2CF2COF、 CF2C1CFC1CF2CF20C0CF2CF2CF2CF2C0F、 (CF3)2CFCF2OCOCF2CF2CF2CF2COF、 CF3CF2CF2OCOCF2CF2CF2CF2COF o 作爲含氟羰基化合物(5)的具體例,可舉出下記化合物及過 氧化環己烷。惟,CYf表示過氟化環己基。 -25- 本紙張尺度適用中國國家標準(CNS〉A4規格(210 X 297公釐) 584628 A7 ___B7 五、發明説明(23 ) (CF3)2CO(5-2)、 CYfCOF、 CF2C1CFC1CF2C0F、 (請先閱讀背面之注意事項再填寫本頁) (CF3)2CFCOF(5-3)、 CF3CF2COF、 CF3CF2CF2OCF(CF3)COF、 CF3CF2CF2OCF(CF3)CF2〇CF(CF3)COF、 CF3CF2CF2OCF2CF2COF。 且’作爲本發明的製造方法,由生成物的有用性及對 過去的製造方法而言較爲優之觀點來看,η爲2,R1與R2 爲-CH3,Rlf與R2f爲-CF3時的化合物(5-2 )製造方法,以 R1 爲-H,R2 爲-CH ( CH3 ) 2,Rlf 爲 ,R2f 爲 _CF ( CF3 ) 2 時的化合物( 5-3)製造方法爲佳。 經濟部智慧財產局員工消費合作社印製 且’作爲化合物(5-2)的製造方法之較佳型態,可舉 出下述製造方法。其中,k表示2〜8的整數,k爲4〜6的 整數因較易得到而較佳。即,化合物(I-2 )與化合物(2-2 )進行酯化反應,得到含有化合物(3 -2 )的酯化反應生成 物’含有該化合物(3 -2 )的酯化反應生成物進行氟化反應 得到經全氟化的含有化合物(4-2 )之氟化反應生成物,該 氟化反應中因進行酯鍵的分解反應,得到含有化合物(5-2 )與化合物(.2-2)的分解反應生成物,由該分解反應生成 物得到化合物(2 - 2 )的方法爲佳。且,由分解反應生成物 得到化合物(2-2 ),將此作爲與化合物(1 -2 )反應之化合 物(2 - 2)使用,經由進行相同反應可連續製造出化合物(5 - 2 -26- 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 584628 A7 B7 五、發明説明(24 ) )爲佳。 (CH3 ) 2CHOH ( 1-2 )、 (請先閲讀背面之注意事項再填寫本頁) FCO(CF2)kCOF(2-2)、 (CH3)2CHOCO(CF2)kCOOCH(CH3)2(3-2)、 (CF3)2CF OCO(CF2)kCOOCF(CF3h(4-2)、 CF3COCF3(5-2)。 化合物(5-2)(即,六氟丙酮。以下以HFA表示)及 化合物(5-3 ),其本身作爲各種中間體係爲有用的公知化 合物,但將此以公知方法還原時可製造出(CF3 ) 2CHOH ( 1,1,1,3,3,3-六氟-2-丙醇,以下以HFIP表示)及 (CF3 ) 2CFCHOH。HFIP亦作爲溶劑及各種中間體時爲有 用的公知化合物。此製造方法的槪念如下所示。CyfOCOCF2CF2CF2CF2COF, CF2C1CFC1CF2CF20C0CF2CF2CF2CF2C0F, (CF3) 2CFCF2OCOCF2CF2CF2CF2CF2COF, CF3CF2CF2OCOCF2CF2CF2CF2COF o As specific examples of the fluorine-containing carbonyl compound (5) and the cyclic oxides, the following can be mentioned. However, CYf stands for perfluorinated cyclohexyl. -25- This paper size applies to Chinese national standards (CNS> A4 size (210 X 297 mm) 584628 A7 ___B7 V. Description of the invention (23) (CF3) 2CO (5-2), CYfCOF, CF2C1CFC1CF2C0F, (Please read first Note on the back page, please fill in this page again) (CF3) 2CFCOF (5-3), CF3CF2COF, CF3CF2CF2OCF (CF3) COF, CF3CF2CF2OCF (CF3) CF2〇CF (CF3) COF, CF3CF2CF2OCF2CF2COF. And 'as the manufacturing method of this invention, From the point of view of the usefulness of the product and its superior manufacturing method, the method for producing compound (5-2) when η is 2, R1 and R2 are -CH3, and Rlf and R2f are -CF3, The compound (5-3) is better when R1 is -H, R2 is -CH (CH3) 2, Rlf is, and R2f is _CF (CF3) 2. It is printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs and 'As a preferable form of the production method of the compound (5-2), the following production methods are mentioned. Among them, k represents an integer of 2 to 8 and k is an integer of 4 to 6 because it is easier to obtain. That is, the compound (I-2) is subjected to an esterification reaction with the compound (2-2) to obtain an esterification reaction containing the compound (3-2). 'The esterification reaction product containing the compound (3-2) is subjected to a fluorination reaction to obtain a perfluorinated fluorination reaction product containing the compound (4-2). In this fluorination reaction, an ester bond is decomposed. The reaction is to obtain a decomposition reaction product containing the compound (5-2) and the compound (.2-2), and a method for obtaining the compound (2-2) from the decomposition reaction product is preferable. Compound (2-2), which is used as the compound (2-2) that reacts with compound (1-2), and the compound (5-2-26-26) can be continuously produced by performing the same reaction. (CNS) A4 specification (210X297 mm) 584628 A7 B7 5. Invention description (24)) is better. (CH3) 2CHOH (1-2), (Please read the precautions on the back before filling this page) FCO (CF2 ) kCOF (2-2), (CH3) 2CHOCO (CF2) kCOOCH (CH3) 2 (3-2), (CF3) 2CF OCO (CF2) kCOOCF (CF3h (4-2), CF3COCF3 (5-2). Compound (5-2) (that is, hexafluoroacetone. Hereinafter referred to as HFA) and compound (5-3) are known compounds useful as various intermediate systems in themselves, but It can be produced (CF3) 2CHOH (1,1,1,3,3,3- hexafluoro-2-propanol, hereinafter referred to as HFIP) when reduced to this known method, and (CF3) 2CFCHOH. HFIP is also a well-known compound useful as a solvent and various intermediates. The idea of this manufacturing method is shown below.
(CH3>2CH〇CO(CF2)4COOCH(CH3)2 fco(cfz)4cof I ^1 (cf3)2CF〇CO(CF2)4COOCF(CF3)2 經濟部智慧財產局員工消費合作社印製 cf3c〇cf3 本發明的製造方法係經由回收生成物等方法而成爲更 有效率之製造方法。以下對有效率之製造方法舉例說明。 且,以下無特別定義的基,則表示與上述相同。 (I )回收化合物(2 )的方法;係使用回收酯鍵的分 解反應生成物中所生成的化合物(2 ),將此作爲與化合物 本紙張尺度適用中.國國家標準(CNS ) A4規格(210X297公t ) ^97 - 584628 A7 _B7_ 五、發明説明(25 ) (請先閱讀背面之注意事項再填寫本頁) (1 )進行酯化反應的化合物(2 )之方法。該方法係爲可 多次利用化合物(2 )的具有經濟性且有效率之方法。作爲 具體例子,可舉出上述HFA製造方法中,回收酯鍵的分解 反應所生成的FC〇(CF2) 4C〇F,與(CH3 ) 2CH0H進行酯 化反應之方法。 (II)氟化反應生成物中含有部分氟化物時,將該部分 氟化物回收於氟化反應系統中的方法;化合物(3 )的氟化 反應的生成物中,有含有化合物(3 )的部分氟化物之情況 。作爲該部分氟化物,可舉出氫殘留化合物(即,化合物 (3 )以至少會剩下1個的氫原子的比率下經氟化之化合物 )。部分氟化物可藉由回到氟化反應的反應系統中再次進 行氟化反應,而成爲化合物(4 )。 例如,化合物(1 )爲(CH3 ) aCHOH,化合物(2 )爲 FCO ( CF2 ) kC〇F 時,作爲(CH3) 2CHOCO ( CF2 ) kCOOCH (CH3 ) 2的部分氟化物之下述化合物爲含於氟化反應生成 物中。 (CF3)2CH〇C〇(CF〇kC〇〇CH(CF3)2、 經濟部智慧財產局員工消費合作社印製 (CF3)2CH〇C〇(CF2)kC〇〇CF(CF3)2、 (CF2H)2CH〇C〇(CF2)kC〇〇CH(CHF2)2。 又,氟化反應生成物中,作爲(CH3 ) 2 CH〇C〇(CF2)k C〇F部分,氟化物之如下記化合物,亦它包含於氟化反應 生成物中。 (CF〇2CH〇C〇(CF〇kCOF、 (CF2H)2CH〇C〇(CF2)kC〇F。 P氏張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) . 經濟部智慧財產局員工消費合作社印製 584628 A7(CH3 > 2CH〇CO (CF2) 4COOCH (CH3) 2 fco (cfz) 4cof I ^ 1 (cf3) 2CF〇CO (CF2) 4COOCF (CF3) 2 Printed by cf3c〇cf3 in the Intellectual Property Bureau of the Ministry of Economy's Consumer Cooperatives) The manufacturing method of the present invention is a more efficient manufacturing method through a method such as recycling a product. The efficient manufacturing method is exemplified below. In addition, if there is no specific definition below, it means the same as above. (I) Recovered compound (2) The method is to recover the compound (2) produced from the decomposition reaction product of the ester bond, and use this as the standard of the compound on this paper. National Standard (CNS) A4 Specification (210X297 Gt) ^ 97-584628 A7 _B7_ V. Description of the invention (25) (Please read the precautions on the back before filling out this page) (1) Method for compound (2) for esterification. This method is a compound that can be used multiple times ( 2) An economical and efficient method. As a specific example, in the HFA production method described above, FC0 (CF2) 4C0F produced by the decomposition reaction of the ester bond is recovered, and esters are formed with (CH3) 2CH0H. Method of chemical reaction (II) Fluorination reaction When a part of the fluoride is contained, the method of recovering the part of the fluoride in the fluorination reaction system; the product of the fluorination reaction of the compound (3) may contain the part of the fluoride of the compound (3). Examples of the partial fluoride include a hydrogen residual compound (that is, a compound fluorinated at a ratio of at least one hydrogen atom remaining in the compound (3). Part of the fluoride can be returned to the fluorination reaction. In the reaction system, the fluorination reaction is performed again to become the compound (4). For example, when the compound (1) is (CH3) aCHOH and the compound (2) is FCO (CF2) kCOF, it is (CH3) 2CHOCO (CF2) The following compounds of partial fluorides of kCOOCH (CH3) 2 are contained in the fluorination reaction product: (CF3) 2CH〇C〇 (CF〇kC〇〇CH (CF3) 2, Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs) (CF3) 2CH0C0 (CF2) kC0CF (CF3) 2, (CF2H) 2CH0C0 (CF2) kC0CH (CHF2) 2. In addition, the fluorination reaction product was used as (CH3) 2 CH0C0 (CF2) kC0F, the following compounds of fluoride, it is also included in the fluorination reaction. (CF〇2CH〇C〇 (CF〇kCOF, (CF2H) 2CH〇C〇 (CF2) kCOF). The P-scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). Ministry of Economy Printed by the Intellectual Property Bureau Employee Cooperatives 584628 A7
五、發明説明(26 ) 這些部分氟化物係可於氟化反應的系統中經回收’而 轉變成完全氟化物。該方法的槪念如下所不。5. Description of the invention (26) These partial fluorides can be recovered 'in the system of the fluorination reaction and converted into complete fluorides. The idea of this method is as follows.
(III )含有部分氟化物的情況下直接進行醋鍵之分解 反應,由反應生成物分離含氟羰基化合物(5)後,回收至 酯化反應的反應系統中之方法; 部分氟化物之中,具有-CF0C〇-部分的化合物’雖可經 酯鍵之分解反應而分解該部分,但不會分解具有-CH〇C〇-部 分之化合物的該部分。不管酯鍵是否被分離’使部分氟化 物存在於酯鍵的分解反應系統中’由生成物分離出含氟羰 基化合物(5 )後,回收至酯化反應的反應系統中’該部分 氟化物會變成化合物(4)。 作爲該方法的具體例子,可舉出生成作爲部分氧化物 之(CF3) 2CHOCO(CF2)kCOOCF(CF3)2,經酯鍵的分解反應得 (CF3) 2CH〇C〇(CF2)kC〇F 進行(CF3)2C = 〇,分離(CF3)2C = 〇 後,將(CF3)2CH〇C〇(CF2)kC〇F與FC〇(CF2)kC〇F同時與 (<:ίί3)2(:ίΙ〇Η[進行反應之方法。該反應之槪念如下所示。 (請先閱讀背面之注意事項再填寫本頁)(III) a method of directly carrying out the decomposition reaction of the vinegar bond in the case of containing a part of fluoride, separating the fluorine-containing carbonyl compound (5) from the reaction product, and recovering it into the reaction system of the esterification reaction; Although a compound having a -CF0C0- moiety can decompose the moiety through an ester bond decomposition reaction, it does not decompose the portion of a compound having a -CH0C0- moiety. Regardless of whether or not the ester bond is separated, 'a part of the fluoride exists in the decomposition reaction system of the ester bond', and after the fluorocarbonyl compound (5) is separated from the product, it is recovered to the reaction system of the esterification reaction. It becomes compound (4). As a specific example of this method, (CF3) 2CHOCO (CF2) kCOOCF (CF3) 2 is generated as a partial oxide, and (CF3) 2CH0C0 (CF2) kC0F is obtained by decomposition reaction of an ester bond. (CF3) 2C = 0, (CF3) 2C = 0, and (CF3) 2CH0C0 (CF2) kC0F and FC0 (CF2) kC0F are simultaneously (<: 3) 2 (: ίΙ〇Η [Method of reaction. The idea of the reaction is shown below. (Please read the precautions on the back before filling this page)
本紙張尺度適用中.國國家標準(CNS ) Α4規格(210X297公釐) -29- 584628 A7 B7 五、發明説明(27 )The size of this paper is applicable. National National Standard (CNS) A4 specification (210X297 mm) -29- 584628 A7 B7 V. Description of invention (27)
(請先閱讀背面之注意事項再填寫本頁) (CH3)2CHOCO(CF2)4COOCH(CH3)2 (C F3)2 CHOC O (C F2hc Ο 0 CH(CHzh(Please read the notes on the back before filling this page) (CH3) 2CHOCO (CF2) 4COOCH (CH3) 2 (C F3) 2 CHOC O (C F2hc Ο 0 CH (CHzh
FCO(CF2)4C〇F 又-f [ (CF3)2CHOCO(CF2)4COF j — (CF3)2CFOCO(CF2〉4COOCF(CF3)2 f 十[(CF3)2CHOCO(CF2〉4COOCF(CF3)2 CF3COCF3 又,生成未分解的如作爲部分氟化物的 (CF; ) 2CHOCO ( CF2) kCOF化合物時,分離此而依據(2 )所說明的方法回收至氟化反應系統中亦可’或未分離而 含於酯鍵的分解反應系統中,再下次酯鍵的分解反應後與 FC〇(CF2 ) kC〇F — 齊回收(CF3 ) 2CH0C0 ( CF2) kC〇F ’ 可 使用於與(CH3 ) 2CH0H之酯化反應亦可。 經濟部智慧財產局8工消費合作社印製 (IV )化合物(3 )進行氟化反應時,於具有對應化合 物(3)的碳骨架,且氟含量比化合物(3)少之化合物存 在下進行氟化之方法;‘ 該方法係爲於氟化反應及酯分解反應的收率較低時特 別有利之方法。其原因爲,實施回收化合物(2 )後使用於 與化合物(1)進行反應之(1)步驟時’實際上一般難使 化合物(2 )的回收率到達100%。故隨著重複連續製造’ 會有與化合物(1 )進行反應的化合物(2 )量減少之問題 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -30 - 584628 A7 B7 五、發明説明(28 ) (請先閱讀背面之注意事項再填寫本頁) 欲解決該問題,於氟化步驟中,與化合物(3 )同時存 在比化合物(3)較少氟含量之化合物(下述以化合物(3H )爲佳)進行氟化反應爲佳。惟,式中記號與上述相同意 義,QH表示以氫原子爲必須之η價有機基,且經全氟化之 Qf的基。FCO (CF2) 4C〇F and -f [(CF3) 2CHOCO (CF2) 4COF j — (CF3) 2CFOCO (CF2> 4COOCF (CF3) 2 f ten [(CF3) 2CHOCO (CF2> 4COOCF (CF3) 2 CF3COCF3 and When a non-decomposed (CF;) 2CHOCO (CF2) kCOF compound is generated as a partial fluoride, it can be separated and recovered in the fluorination reaction system according to the method described in (2). In the ester bond decomposition reaction system, after the next ester bond decomposition reaction, it will be recovered with FC〇 (CF2) kC〇F-(CF3) 2CH0C0 (CF2) kCOF 'can be used for the ester with (CH3) 2CH0H The chemical reaction is also available. When the compound (3) printed by (IV) Industrial Cooperative Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs has a fluorination reaction, it has a carbon skeleton corresponding to the compound (3), and the fluorine content is less than the compound (3) A method for performing fluorination in the presence of a compound; 'This method is a particularly advantageous method when the yields of the fluorination reaction and the ester decomposition reaction are low. The reason is that the compound (2) is used for recovery with the compound (1) ) When performing step (1) of the reaction, 'it is generally difficult to make the recovery of compound (2) reach 100%. Repeated and continuous manufacturing 'There will be a problem of reducing the amount of compound (2) which reacts with compound (1) This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -30-584628 A7 B7 V. Description of the invention ( 28) (Please read the precautions on the back before filling this page) To solve this problem, in the fluorination step, a compound with a lower fluorine content than the compound (3) is present at the same time as the compound (3) (the following compounds ( 3H) is preferred) The fluorination reaction is preferably performed. However, the symbol in the formula has the same meaning as above, QH represents a group of a η-valent organic group which requires a hydrogen atom and is fully fluorinated.
QH(COOCHR1R2)m(COF)n.m····.·式 3H 對於氟化反應以液相氟化反應進行時,因化合物(3H )於單獨下難以溶解於液相者,故經由與具類似構造的化 合物(3 )共存下,有著提高對液相之溶解性的優點。特別 爲QH爲具有酯鍵的基時,有著更提升化合物(3)或化合 物(3H )之溶解性的優點。化合物(3H ),由經濟性的觀 點來看,以未含氟的化合物爲佳。 化合物(3)爲化合物(3-1)時,作爲化合物(3H) 的具體例子可舉出下述化合物(3H-1)。惟,QH2表示以氫 原子爲必須之2價有機基,且經全氟化之Qf2的基。 R^HR^COQ^COOCHR^2·····.式(3H-1) 經濟部智慧財產局員工消費合作社印製 QH2爲對應Qf2的具有碳骨架的不含氟的2價有機基爲 佳,特別爲伸烷基、伸烷基的碳-碳鍵結間插入醚性氧原子 爲佳。 作爲化合物(3H-1)的具體例子,可舉出 (CH3)2CH〇C〇(CH2)kC〇〇CH(CH3)2。化合物(3-1 )的存在下 實施連續反應方法之槪念如下所示。 -31 - 本紙張尺度適用中.國國家標準(CNS ) A4規格(210X297公釐) 584628 A7 B7 五、發明説明(29 )QH (COOCHR1R2) m (COF) nm ······························································································································· The coexistence of the structured compound (3) has the advantage of improving solubility in the liquid phase. In particular, when QH is a group having an ester bond, there is an advantage that the solubility of the compound (3) or the compound (3H) is further improved. From the viewpoint of economy, the compound (3H) is preferably a compound containing no fluorine. When the compound (3) is the compound (3-1), specific examples of the compound (3H) include the following compound (3H-1). However, QH2 represents a divalent organic group which requires a hydrogen atom and is a perfluorinated Qf2 group. R ^ HR ^ COQ ^ COOCHR ^ 2 ···· .. Formula (3H-1) QH2 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is a non-fluorine-containing bivalent organic group with a carbon skeleton corresponding to Qf2. In particular, it is preferable to insert an etheric oxygen atom between the carbon-carbon bonds of the alkylene group and the alkylene group. Specific examples of the compound (3H-1) include (CH3) 2CHOC (CH2) kCO (CH3) 2. The idea of carrying out the continuous reaction method in the presence of the compound (3-1) is shown below. -31-This paper is applicable in China National Standard (CNS) A4 specification (210X297mm) 584628 A7 B7 V. Description of invention (29)
(請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製(Please read the notes on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs
對化合物(3 )的化合物(3H )量,對於氟化反應而言 僅非不適量即可無特別限定。氟化反應於液相氟化反應中 實施時,化合物(3)與化合物(3H)雙方可充分溶解於液 相中的範圍即可無特別限制,對於化合物(3 )而言化合物 (3H)的量爲0.001倍莫耳〜〇.2倍莫耳爲佳。又,化合物 (3H )與化合物(3 )的總量,於氟化溶劑中爲5重量%以 下爲佳,0.5重量%以下更佳。 化合物(3H)可於市販品或其他合成者存在於氟化步 驟前的系統中進行酯化反應、或與化合物(2 )同時存在下 述化合物(2H )進行酯化反應亦可。但,式中的記號與上 述相同。 QH(C〇F)n...S2H 化合物(2H )與化合物(1 )的酯化反應,一般爲與化 合物(2 )與化合物(1 )酯化反應同時進行。化合物(2H 本紙張尺度適用中國國家標隼(CNS )八4規格(210X 297公釐) -32- 584628 經濟部智慧財產局員工消費合作社印製 A7 ___ B7 五、發明説明(30 ) )的具體例子,可舉出下述化合物(2H-1)。惟,X表示鹵 素原子或羥基。 XC〇(CH2) kC〇F···式(2H-1) 存在化合物(2H )下進行反應的具體例子如下所示。 ! H0OC(CH2)4C00H (CH3)2CHOCO(CH2)4COOCH(CH3)2 + + (CH3)2CHOH / (CH3)2CHOCO(CF2〉4COOCH(CH3)3 FCO<CF2)4COF V --- (CF3)2CFOCO(CF2)4COOCF(CF3)2 CF3COCF3 本發明的製造方法所得之含氟羰基化合物(5 )之用途 雖無特別限定。該化合物可直接使用,或使用於其他種種 用途上。例如,還原含氟羰基化合物(5)可製造種種有用 的含氟醇。 實施例 以下對本發明做詳細說明,但本發明不受這些限定。 且,如下所述,1,1,2-三氯-1,2,2-三氟乙烷以R-113表示, 壓力爲表壓。又,氣相色譜法以GC做表示,GC分析的波 峰面積比以GC分析値表示。又,氣相色譜質量分析以GC-MS表示。NMR的波峰面積以比表示。 本紙張尺度適用中國國家榡準(CNS ) A4規格(210 X 297公釐) -33 -The amount of the compound (3H) of the compound (3) is not particularly limited as long as it is not an unsuitable amount for the fluorination reaction. When the fluorination reaction is carried out in the liquid phase fluorination reaction, the range in which both the compound (3) and the compound (3H) can be sufficiently dissolved in the liquid phase is not particularly limited. For the compound (3), the compound (3H) The amount is preferably 0.001 times mole to 0.2 times mole. The total amount of the compound (3H) and the compound (3) is preferably 5% by weight or less, and more preferably 0.5% by weight or less in a fluorinated solvent. The compound (3H) may be esterified in a commercially available product or other synthesizers before the fluorination step, or the compound (2H) may be esterified in the presence of the compound (2). However, the symbols in the formula are the same as above. QH (CoF) n ... S2H The esterification reaction of the compound (2H) and the compound (1) generally proceeds simultaneously with the esterification reaction of the compound (2) and the compound (1). Compound (2H) This paper size is applicable to China National Standard (CNS) VIII (210X 297mm) -32- 584628 Printed by A7 ___ B7 of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. The specific description of the invention (30) Examples include the following compound (2H-1). However, X represents a halogen atom or a hydroxyl group. XC〇 (CH2) kCOF ... Formula (2H-1) A specific example of a reaction in the presence of a compound (2H) is shown below. ! H0OC (CH2) 4C00H (CH3) 2CHOCO (CH2) 4COOCH (CH3) 2+ + (CH3) 2CHOH / (CH3) 2CHOCO (CF2> 4COOCH (CH3) 3 FCO < CF2) 4COF V --- (CF3) 2CFOCO (CF2) 4COOCF (CF3) 2 CF3COCF3 The use of the fluorine-containing carbonyl compound (5) obtained by the production method of the present invention is not particularly limited. The compound can be used directly or used in a variety of other applications. For example, reduction of the fluorine-containing carbonyl compound (5) can produce various useful fluorine-containing alcohols. Examples The present invention is described in detail below, but the present invention is not limited by these. In addition, as described below, 1,1,2-trichloro-1,2,2-trifluoroethane is represented by R-113, and the pressure is a gauge pressure. In addition, gas chromatography is shown by GC, and the peak area ratio of GC analysis is shown by GC analysis. The gas chromatography mass analysis is shown by GC-MS. The peak area of NMR is expressed as a ratio. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -33-
(請先閱讀背面之注意事項再填寫本頁) 584628 A7 B7 五、發明説明(31 ) 〔實施例1〕( CF3) 2C0的製造例 〔例1-1〕 ( CH3) 2CH〇H與FC〇(CF2) 4C〇F的酉旨化反 (請先閱讀背面之注意事項再填寫本頁) 應 耐熱耐蝕鎳基合金C製的2L的高壓鍋中放入 (CH3 ) 2CHOH ( 600g)。冷卻反應器,常壓下保持內溫30 °C以下將FCO ( CFO 4COF ( 1540g)慢慢導入。邊充分攪拌 邊使氮氣冒泡,將反應所產生的HF釋出系統化。投入全量 FC〇(CFa ) 4C〇F後,再進行50°C的5小時反應得到生成物 。生成物經GC分析結果,生成98.9%的 (CH3)2CH〇C〇(CF2)4 (C〇〇CH(CH3)2,1.1%的 ((^3)2(:11〇(:〇(。?2)4。〇?,未檢測出未反應的異丙基醇,該生 成物無須純化,使用於以下反應。 (CH3)2CH〇C〇(CF2)4CO〇CH(CH3)2 的光譜數據; j-NMRUOOJMHz ,溶劑:CDCh ,基準:TMS) 5 (ppm):1.40(d,6H)、5.21(m,lH)。 19F-NMR(282.7MHz、溶劑:CDCh ,基準:CFCh) 5 (ppm): 119.5、123.1、 經濟部智慧財產局員工消費合作社印製 〔例1-2〕經氟化反應的(Please read the precautions on the back before filling in this page) 584628 A7 B7 V. Description of the invention (31) [Example 1] (CF3) Manufacturing example of 2C0 [Example 1-1] (CH3) 2CHOH and FC. (CF2) 4C0F's purpose (Please read the precautions on the back before filling out this page) Put 2CHH (600g) in a 2L autoclave made of heat-resistant and corrosion-resistant nickel-based alloy C. Cool the reactor and keep the internal temperature below 30 ° C under normal pressure. Slowly introduce FCO (CFO 4COF (1540g). While fully stirring while bubbling nitrogen, the HF produced by the reaction is released systematically. Full amount of FC is introduced. After (CFa) 4C0F, a reaction was performed at 50 ° C for 5 hours to obtain a product. GC analysis of the product yielded 98.9% of (CH3) 2CHOC (CF2) 4 (C〇CH (CH3) ) 2, 1.1% of ((^ 3) 2 (: 11〇 (: 〇 (?? 2) 4.〇 ?, no unreacted isopropyl alcohol was detected, and the product did not require purification, and was used in the following reaction (CH3) 2CH0C0 (CF2) 4CO0CH (CH3) 2 spectral data; j-NMRUOOJMHz, solvent: CDCh, reference: TMS) 5 (ppm): 1.40 (d, 6H), 5.21 (m, lH). 19F-NMR (282.7MHz, solvent: CDCh, reference: CFCh) 5 (ppm): 119.5, 123.1, printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs [Example 1-2]
(CF3) 2CF0C0 ( CFi) 4 C〇〇CF ( CF3) 2 的製造伊J 於500mL的鎳製高壓鍋中放入R- 113 ( 200g)後,邊攪 拌邊保持25 °C。高壓鍋氣體出口直列設置保持20°C的冷卻 器、NaF原料塡充塔、及保持-l〇°C的冷卻器。又,設置欲 指保持-l〇°C的冷卻器所凝集的液體回到高壓鍋之液體回送 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) „ 34 - 584628 A7 B7 五、發明説明(32 ) 路線。於室溫下吹入氮氣1小時後,將以氮氣稀釋至20% 的氟氣(以下表示20%稀釋氟氣)於室溫下以流速9.76L/h 吹入1小時。再邊將20%稀釋氟氣以相同流速吹入,邊將 例1-丨所得之生成物(7g)溶解於R-113 ( 140g)之溶液經 6.1小時注入。 繼續,邊以相同流速吹入20%稀釋氟氣,邊提高高壓 鍋的內壓力至〇.15MPa,苯濃度爲0.01 g/mL的R-113溶液 邊由25°C升至40°C而注入9mL,封閉高壓鍋的苯溶液注入 口,繼續攪拌0.3小時。 再將反應器內壓保持於〇.15MPa,反應器內溫度保持於 40°C而注入6ml的上述苯溶液,封閉高壓鍋的苯溶液注入 口,繼續攪拌0.3小時。同樣操作重複3次。苯的注入總量 爲0.34g,R-113的注入總量爲33mL。 且,邊以相同流速吹入20%稀釋氟氣,邊繼續攪拌1.1 小時。繼續將反應器內壓力作爲常壓,氮氣吹入2小時, 由得到的混合物除去R-113得到生成物(14. lg)。生成物 經19F-NMR分析結果確認含標記化合物的收率爲23.5%。 又,生成物中,例1-1所得之生成物的部分氟化物含有1種 以上(合計收率爲67.7% )。該氟化反應生成物可直接使 用於以下反應中。 19F-NMR(282.7MHz、溶劑:CDCh ,基準:CFCh) 5 (ppm):-79.3(12F)、-118.7(4F)、-122.5(4F)、142.8(2F)。 〔例1-3〕酯鍵的分解反應 :扶4本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) I--------9-辦衣— (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 -35- 584628 A7 B7 五、發明説明(33 ) 備有蒸餾塔及可經冷水冷卻的李比希冷凝器之餾出路 線、接受器、及乾冰凝氣閥備於反應容器上部之20ml反應 容器中,放入KF ( 0.7g) ,150°C加熱。反應容器中慢慢添 加例1-2所得之氟化反應生成物。添加終了後1小時,無氣 體產生時即反應終了。接受器中回收5.82g的生成物。生成 物爲含有FC〇(CF2)4COF(GC收率29%)進行 FC〇(CF2)4 C〇〇CH(CF3)2(GC收率60%)。又,反應容器中生 成以(CF3 ) 2CH〇C〇(CF2)4C〇〇CH(CF3)2爲主成分之液體 (4.10g)。又,凝氣閥中GC純度爲95%(CF3)2CO(3.74(g)被回 收。 〔例 1-4〕經氟化反應的(CF) 2CFOCO ( CF2) 4COOCF (CF3 ) 2 3L的鎳製高壓鍋中,作爲氟化反應溶劑加入 CFs ( CF2 ) 2〇CF ( CF3 ) CF2OCF ( CF3 ) COF ( 2534g )攪拌 ,保持25°C。高壓鍋氣體出口設置保持-l〇°C的冷卻器。氮 氣吹入3.5小時後,將氮氣稀釋至50%的氟氣(以下表示 50%稀釋氟氣)以流速94.89L/h吹入2小時。再邊將50% 稀釋氟氣以相同流速吹入,邊將含例1-1所得之生成物( CHs) 2CHOCO ( CF2) 4COOCH ( CH3) 2 ( 7g) ( 943g)之生 成物經20.0小時注入。取出1523g的反應粗液。 繼續,邊以相同流速吹入50%稀釋氟氣,同時與含有 例卜1所得之(CH3 ) 2CH〇C〇(CF! ) 4C〇〇CH ( CEh ) 2 ( 9 5 3 g )生成物與(CH3 ) 2CH〇C〇(CH2 ) 4C〇〇CH ( CH3 ) 2 ( 本紙張尺度適用中國國家標準(CNS ) A4規格(210 X297公釐) _ 36 - (請先閱讀背面之注意事項再填寫本頁) •裝· 訂 經濟部智慧財產局8工消費合作社印製 584628 A 7 B7 五、發明説明(34 ) 3〇2)經21.8小時注入,取出反應粗液(1612£)。 (請先閱讀背面之注意事項再填寫本頁) 且,邊以相同流速吹入50%稀釋氟氣,同時與含有例 1-1 所得之(CH3 ) 2CHOCO ( CF2 ) 4COOCH ( CHs ) 2 ( 946g )生成物與(CHs ) aCHOCO ( CHa ) 4COOCH ( CH3 ) a ( 58g )經23.2小時注入。 繼續,邊以相同流速吹入50%稀釋氟氣,邊調整爲3 小時。再吹入氮氣3小時,回收反應粗液(4212g)。對各 反應粗液進行GC-MS分析結果,得到含有以標記化合物作 爲主生成物的 CF3CF2CF2OCF ( CF3 ) CF2OCF ( CFs ) COF 與 標記化合物之生成物。 〔例1-5〕經酯鍵的分解反應之(CF3) 2CO製造例 備有蒸餾塔及可經冷水冷卻的李比希冷凝器之餾出路 線、接受器、及乾冰凝氣閥備於反應容器上部之300ml反 應容器中,放入KF ( 29g) ,150°C加熱。反應容器中經10 小時以313g/小時添加例1-2所得之含 經濟部智慧財產局員工消費合作社印製 (CF3) 2CF〇C〇(CF2) 4COCF ( CF3) 2 之生成物。添力D終了 後1小時,反應容器中無氣體產生時即反應終了。接受器 回收CF純度爲98%的FCO ( CF2) 4COF。又,凝氣閥回收 CF 純度爲 95% 的(CF3) 2CO ( 1505g)。 〔參考例1〕經(CF3) 2CO的還原反應之 (CF3) 2CHOH的製造例 將例1-3所得之GC純度95%的(CF3 ) 2CO以Trap-T〇- -37- 沾3本紙張尺度適用中周國家標準(〇奶)八4規格(210\297公釐) 584628 A7 ___B7_ 五、發明説明(35 ) (請先閲讀背面之注意事項再填寫本頁)(CF3) 2CF0C0 (CFi) 4 Co. CF (CF3) 2 Manufacture In a 500 mL nickel autoclave, R-113 (200g) was placed, and then kept at 25 ° C while stirring. The autoclave gas outlet is provided with a cooler maintained at 20 ° C, a NaF raw material charging tower, and a cooler maintained at -10 ° C. In addition, the setting is to return the liquid condensed by the cooler kept at -10 ° C to the liquid return of the autoclave. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm). 34-584628 A7 B7 V. Invention Explanation (32) course. After blowing nitrogen at room temperature for 1 hour, the fluorine gas diluted with nitrogen to 20% (hereinafter referred to as 20% diluted fluorine gas) is blown at room temperature at a flow rate of 9.76 L / h for 1 hour. Then, while blowing 20% diluted fluorine gas at the same flow rate, the solution obtained by dissolving the product (7g) obtained in Example 1- 丨 in R-113 (140g) was injected for 6.1 hours. Continue, blowing at the same flow rate Add 20% diluted fluorine gas, while increasing the internal pressure of the autoclave to 0.15 MPa, R-113 solution with a benzene concentration of 0.01 g / mL, while injecting 9 mL from 25 ° C to 40 ° C, closed the autoclave benzene solution injection At the inlet, stirring was continued for 0.3 hours. The internal pressure of the reactor was maintained at 0.15 MPa, and the temperature in the reactor was maintained at 40 ° C, and 6 ml of the benzene solution was injected. The benzene solution injection port of the autoclave was closed, and the stirring was continued for 0.3 hours. The operation was repeated 3 times. The total injection amount of benzene was 0.34g, and the total injection amount of R-113 33mL. In addition, while blowing 20% diluted fluorine gas at the same flow rate, continue to stir for 1.1 hours. Continue to use the internal pressure of the reactor as normal pressure and nitrogen for 2 hours to remove R-113 from the obtained mixture to obtain a product ( 14. lg). As a result of 19F-NMR analysis of the product, it was confirmed that the yield of the labeled compound was 23.5%. In the product, one or more kinds of partial fluorides of the product obtained in Example 1-1 (total yield) 67.7%). The fluorinated reaction product can be directly used in the following reactions. 19F-NMR (282.7MHz, solvent: CDCh, reference: CFCh) 5 (ppm): -79.3 (12F), -118.7 (4F) , -122.5 (4F), 142.8 (2F). [Example 1-3] Decomposition reaction of ester bond: 4 paper sizes are applicable to China National Standard (CNS) A4 specification (210X297 mm) I ------ --9-Handling— (Please read the notes on the back before filling this page) Order printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs-35- 584628 A7 B7 V. Invention Description (33) Equipped with distillation tower and can Cold water-cooled Liebich condenser distilling route, receiver, and dry ice condensate valve 20ml reaction prepared in the upper part of the reaction vessel Put KF (0.7g) in the container and heat it at 150 ° C. The fluorination reaction product obtained in Example 1-2 was slowly added to the reaction container. One hour after the end of the addition, the reaction was completed when no gas was generated. Acceptor The product was recovered in an amount of 5.82 g. The product was FC0 (CF2) 4COF (GC yield 29%), and FC0 (CF2) 4 COCH (CF3) 2 (GC yield 60%) was obtained. In addition, a liquid (4.10 g) containing (CF3) 2CHOC (CF2) 4COOCH (CF3) 2 as a main component was produced in the reaction vessel. The GC purity of the gas trap was 95% (CF3) 2CO (3.74 (g)). [Example 1-4] (CF) 2CFOCO (CF2) 4COOCF (CF3) 2 3L made of nickel after fluorination In a pressure cooker, CFs (CF2) 2〇CF (CF3) CF2OCF (CF3) COF (2534g) was added as a fluorination reaction solvent, and the temperature was maintained at 25 ° C. The autoclave gas outlet was set to a cooler maintained at -10 ° C. Nitrogen blowing After 3.5 hours, the nitrogen gas is diluted to 50% fluorine gas (hereinafter referred to as 50% diluted fluorine gas) and blown in at a flow rate of 94.89 L / h for 2 hours. Then, while 50% diluted fluorine gas is blown in at the same flow rate, The product containing the product (CHs) 2CHOCO (CF2) 4COOCH (CH3) 2 (7g) (943g) obtained in Example 1-1 was injected over 20.0 hours. 1523 g of the reaction crude liquid was taken out. Continue, blowing at the same flow rate 50% dilution of fluorine gas, and (CH3) 2CHOCO (CF!) 4COOCH (CEh) 2 (953) g obtained from Example 1 and (CH3) 2CHOCO ( CH2) 4C〇CH (CH3) 2 (This paper size applies Chinese National Standard (CNS) A4 specification (210 X297 mm) _ 36-(Please read the precautions on the back before filling this page) • Binding and ordering Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, 8th Industrial Cooperative, 584628 A 7 B7 V. Description of the invention (34) 3〇2) After 21.8 hours injection, take out the reaction crude solution (1612 £). (Please read the notes on the back before filling (This page) Also, while blowing 50% of the diluted fluorine gas at the same flow rate, it was mixed with the (CH3) 2CHOCO (CF2) 4COOCH (CHs) 2 (946g) product and (CHs) aCHOCO (CHa) ) 4COOCH (CH3) a (58g) was injected over 23.2 hours. Continue to adjust to 3 hours while blowing 50% diluted fluorine gas at the same flow rate. Then nitrogen was blown for 3 hours to recover the crude reaction liquid (4212g). As a result of GC-MS analysis of each reaction crude liquid, a product containing CF3CF2CF2OCF (CF3) CF2OCF (CFs) COF containing the labeled compound as the main product and the labeled compound was obtained. [Example 1-5] The decomposition reaction through an ester bond (CF3) 2CO manufacturing example has a distillation tower and a cold water-cooled Liebich condenser distillation line, receiver, and dry ice condensate valve are placed in a 300ml reaction container at the top of the reaction container, and put into KF (29g), Heat at 150 ° C. The reaction container containing the product printed in Example 1-2 at 313 g / hour for 10 hours was printed with (CF3) 2CFOC (CF2) 4COCF (CF3) 2 produced by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. One hour after the end of Tim D, the reaction was completed when no gas was generated in the reaction vessel. The receiver recovered FCO (CF2) 4COF with a purity of 98% CF. The condensate valve recovered (CF3) 2CO (1505g) with a purity of 95% CF. [Reference Example 1] Production Example of (CF3) 2CHOH After Reduction of (CF3) 2CO The (CF3) 2CO with 95% GC purity obtained in Example 1-3 was treated with 3 sheets of Trap-T0- -37- The scale is applicable to the National Standard (0 milk) and 8 specifications (210 \ 297 mm) 584628 A7 ___B7_ V. Description of the invention (35) (Please read the precautions on the back before filling this page)
Trap法純化得到GC純度爲99.5%的(CF3 ) 2C〇。將10g的 碳載持3%鈀觸媒塡充於內徑i〇mm的耐熱玻璃管中,以 10g/小時供給GC濃度爲99.5%的(CF3) 2C〇,並供給對( CF3) 2C〇而言2莫耳的氫。接觸時間爲1〇秒、反應溫度爲 150°C。經還原反應得到(CF3) 2CHOH。反應轉化率爲99.8 %,選擇率爲99%。 〔例2〕 ( CF3) 2CFC〇F的製造例 〔例 2-1〕 ( CH3) 2CHCH2〇H 與 FCO ( CF2) 3COF 的酉旨 化反應 經濟部智慧財產局員工消費合作社印製 耐熱耐蝕鎳基C合金製的2L的高壓鍋中放入 (CHO 2CH〇H ( 700g )。冷卻反應器,氮氣密封下,保持 內溫30°C以下將FCO ( CF2 ) 3C〇F ( 1190g )慢慢導入。投 入全量FCO ( CF2) 3COF後,再進行50°C的5小時反應得 到生成物,在經氮氣冒氣將副產物的HF排出系統外,得到 生成物。生成物經GC分析結果,生成98.7%的 (CH3)2CHCH2〇C〇(CF2)3C〇〇CH2CH(CH3)2、1.3%的 (CH3)2 CHCHaOCO (CF2) 3C〇F未檢測出未反應的異丁基醇。 該生成物無須純化而使用於以下反應。 3H-NMR(300.4MHz ,溶劑:CDCh ,基準:TMS) δ (ppm):0.98(d,6H)、2.06(m,lH)、4.15(d,2H)。 19F-NMR(282.7MHz、溶劑:CDC13 ,基準:CFC13) 5 (ppm):-118.9、-124.3。 本紙張尺度適用中.國國家標準(CNS ) A4規格(210X297公釐) 584628 A7 B7 五、發明説明(36 ) 〔例2-2〕經氟化反應的(CF3 ) 2CFCF2〇C〇(CF2 ) 3CO〇CF2CF ( CF3) 2的製造例 (請先閲讀背面之注意事項再填寫本頁) 準備使用於例1-2反應裝置相同之鎳製高壓鍋,放入 R-113 ( 312g)後,20%稀釋氟氣以流速10.60L/h吹入之 外,其他與例1-2相同條件。該高壓鍋中經5.5小時注入例 2-1所得的生成物(5g)溶解於R_113 ( 95g)之溶液。 繼續,邊以相同流速吹入20%稀釋氟氣,邊提高高壓 鍋的內壓力至0.15MPa,苯濃度爲0.01g/mL的R-113溶液 邊由25°C升至40°C而注入9mL,封閉高壓鍋的苯溶液注入 口,繼續攪拌0.3小時。 再將反應器內壓保持於0.1 5MPa,反應器內溫度保持於 40°C而注入6ml的上述苯溶液,封閉高壓鍋的苯溶液注入 口,繼續攪拌0.3小時。同樣操作重複3次。苯的注入總量 爲0.22g,R-113的注入總量爲22mL。 且,邊以相同流速吹入20%稀釋氟氣,邊繼續攪拌1.0 小時。繼續將反應器內壓力作爲常壓,氮氣吹入1.0小時。 生成物經19F-NMR分析結果確認含標記化合物的收率爲87 經濟部智慧財產局員工消費合作社印製 19F-NMR(282.7MHz、溶劑:CDC13,基準:CFC13) 5 (ppm) :-73.8(12F)、-80.5(4F)、-118.6(4F)、-123.6(2F)、-187.9(2F) o 〔例2-3〕經由酯鍵的分解反應的(CF3) 2CFCOF的製 造例 本紙張尺度適用中.國國家標準(CNS ) A4規格(210>< 297公釐) 〇9- 584628 A7 __B7 五、發明説明(37 ) (請先閲讀背面之注意事項再填寫本頁) 備有蒸餾塔及可經冷水冷卻的李比希冷凝器之餾出路 線、接受器、及乾冰凝氣閥備於反應容器上部之20ml反應 容器中,放入KF ( 0.7g) ,150°C加熱。反應容器中慢慢添 加除去例7所得之氟化反應生成物r_i π之液體9g。添加 終了後1小時,無氣體產生時即反應終了。接受器中回收 5.72g的生成物。 生成物爲含有 FCO(CF〇3COF(GC面積 55%)進行 FC〇(CF2)3CO〇CF2CH(CF3)2(GC 面積 15%)、(CF〇2CFC〇F(GC 面積30%)。又,凝氣閥中GC純度爲97%(CF3)2CFC〇F (3.12%)被回收。 [例2-4](CH3)2CHCH2〇H進行FC〇(CF2)2C〇F的酯化反應 例2-1中除變更C〇(CF2)3C〇F進行FC〇(CF2)2C〇F(950g) 以外其他與2-1相同進行反應。生成物經GC分析結果,生 成 98.8% 的(CH3)2CHCH2〇C〇(CF2)2C〇〇CH2CH(CH3)2、 1.2% 的 (CH^CHdOCCKCF + COF未檢測出未反應的異丁基醇。該 生成物無須純化使用於以下反應。 經濟部智慧財產局員工消費合作社印製 W-NMRUOOdMHz ,溶劑:CDCh ,基準:TMS) 5 (ppm):0.98(d,6H)、2.05(m,lH)、4.13(d,2H卜 -19F-NMR(282.7MHz、溶劑:CDCh ,基準:CFCh) 5 (ppm):-120.2 〇 [例 2-5]經氟化反應之(CF3)2CFCF2〇C〇(CF2)2 C〇〇CF2CF(CF〇2的製造侈!1 。 本紙張尺度適用中國國家標準(CNS ) Μ規格(210X297公釐) -40 - 584628 A7 B7 五、發明説明(38 ) 準備使用於例1-2反應裝置相同之鎳製高壓鍋,放入 R-113 ( 312g)後,20%稀釋氟氣以流速12.16L/h吹入之 外,其他與例1-2相同條件。該高壓鍋中經5.7小時注入例 2-4所得的生成物(5g)溶解於R-113 ( 100g)之溶液。 繼續,邊以相同流速吹入20%稀釋氟氣,邊提高高壓 鍋的內壓力至〇.15MPa,苯濃度爲0.01g/mL的R-113溶液 邊由25°C升至40°C而注入9mL,封閉高壓鍋的苯溶液注入 口,繼續攪拌0.3小時。 再將反應器內壓保持於0.15MPa,反應器內溫度保持於 40°C而注入6ml的上述苯溶液,封閉高壓鍋的苯溶液注入 口,繼續攪拌0·3小時。同樣操作重複3次。苯的注入總量 爲0 · 2 2 g,R -11 3的注入總量爲21 m L。 且,邊以相同流速吹入20%稀釋氟氣,邊繼續攪拌1.0 小時。繼續將反應器內壓力作爲常壓,氮氣吹入1.0小時。 生成物經19F-NMR分析結果確認含標記化合物的收率爲90 % 〇 19F-NMR(282.7MHz 、溶劑:CDCh ,基準:CFCl3) 5 (ppm):-73.8(12F)、-80,4(4F)、-119.2(4F)、-187.8(2F)。 〔例2-6〕經由酯鍵的分解反應的(CF3) 2CFC〇F的製 造例 將例2-3的氟化反應生成物變更爲例2-5所得之氟化反 應生成物,慢慢添加除去該氟化反應生成物的R11 3的液體 8. lg之外其他進行相同反應。接受器中回收l.〇2g的生成物 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) —--------裝-- (請先閲讀背面之注意事項再填寫本頁) 、11 經濟部智慧財產局員工消費合作社印製 -41 - 584628 A7 B7 五、發明説明(39 ) (請先閲讀背面之注意事項再填寫本頁) 。生成物爲含有 FC〇(CF2)2C〇F(GC 面積 35%)進行 FC〇(CF2)2C〇〇CF2CH(CF3)2(GC 面積 60%)、(CF3)2CFC〇F(GC 面積5%)。凝氣閥中回收6.94g。生成物爲含有FC〇(CF2)2 C〇F(GC 面積 30%)進行(CF3)2CFC〇F(GC 面積 70%)。 產業上可利用性 本發明製造方法的原料之化合物(1),係爲具有碳骨 架的種種化合物之市販品,其可便宜地取得。因此,本發 明製造方法可由此原料化合物,以短步驟且高收率下自由 地製造出具有多樣骨架的含氟化合物。 又,經由使用本發明方法,可容易合成過去方法難以 取得之低分子含氟化合物或複雜構造之含氟化合物。又, 作爲本發明製造方法係爲,並無限定於作爲上述具體例子 所記載的化合物,而可應用於種種其他化合物之廣用性優 良的方法。又,本發明的方法,可經由使用回收化合物等 方法,成爲更具工業上可利用性且有效率之製造方法。 經濟部智慧財產局員工消費合作社印製 -42- 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐)Purification by Trap method gave (CF3) 2CO with a GC purity of 99.5%. 10 g of carbon-supported 3% palladium catalyst was filled into a heat-resistant glass tube with an inner diameter of 10 mm, and (CF3) 2C0 with a GC concentration of 99.5% was supplied at 10 g / hour, and (CF3) 2C was supplied. In terms of 2 moles of hydrogen. The contact time was 10 seconds and the reaction temperature was 150 ° C. (CF3) 2CHOH was obtained by reduction. The reaction conversion was 99.8% and the selectivity was 99%. [Example 2] (Example of manufacturing of CF3) 2CFC〇F [Example 2-1] (CH3) 2CHCH20H and FCO (CF2) 3COF The reaction to the degeneration of the Ministry of Economic Affairs Intellectual Property Bureau Employee Consumer Cooperative printed a heat-resistant and corrosion-resistant nickel-based C alloy 2L autoclave (CHO 2CHOH (700g). Cool the reactor and seal with nitrogen and keep the internal temperature below 30 ° C. FCO (CF2) 3COF (1190g) is slowly introduced. Put After the full amount of FCO (CF2) 3COF, the reaction was performed at 50 ° C for 5 hours to obtain the product, and the by-product HF was discharged out of the system through nitrogen gas. The product was obtained by GC analysis, and 98.7% of the product was produced. (CH3) 2CHCH2OCO (CF2) 3COOCH2CH (CH3) 2, 1.3% (CH3) 2 CHCHaOCO (CF2) 3COF) No unreacted isobutyl alcohol was detected. This product was obtained without purification The following reactions were used: 3H-NMR (300.4 MHz, solvent: CDCh, reference: TMS) δ (ppm): 0.98 (d, 6H), 2.06 (m, 1H), 4.15 (d, 2H). 19F-NMR ( 282.7MHz, solvent: CDC13, benchmark: CFC13) 5 (ppm): -118.9, -124.3. This paper size is applicable. National National Standard (CNS) A4 specification (210X297 mm) 584628 A7 B7 Explanation of the invention (36) [Example 2-2] Production example of (CF3) 2CFCF2〇C〇 (CF2) 3CO〇CF2CF (CF3) 2 after fluorination (please read the precautions on the back before filling this page) A nickel pressure cooker with the same reaction device as in Example 1-2 was prepared. After putting R-113 (312g), a 20% diluted fluorine gas was blown in at a flow rate of 10.60 L / h. The other conditions were the same as in Example 1-2. A solution of the product (5 g) obtained in Example 2-1 and dissolved in R_113 (95 g) was injected into the autoclave over 5.5 hours. Continue, while blowing 20% diluted fluorine gas at the same flow rate, while increasing the inner pressure of the autoclave to 0.15 MPa The R-113 solution with a benzene concentration of 0.01 g / mL was injected from 9 ° C to 25 ° C to 40 ° C. The benzene solution injection port of the autoclave was closed, and the stirring was continued for 0.3 hours. Then, the internal pressure of the reactor was maintained at 0.1 5 MPa. The temperature in the reactor was maintained at 40 ° C and 6 ml of the above benzene solution was injected. The benzene solution injection port of the autoclave was closed, and the stirring was continued for 0.3 hours. The same operation was repeated 3 times. The total amount of benzene injection was 0.22 g. The total injection volume was 22 mL, and stirring was continued for 1.0 hour while blowing 20% diluted fluorine gas at the same flow rate. The pressure in the reactor was continued as normal pressure, and nitrogen was blown in for 1.0 hour. 19F-NMR analysis of the product confirmed that the yield of the labeled compound was 87. 19F-NMR (282.7MHz, solvent: CDC13, standard: CFC13) printed by the Consumer Cooperatives of Intellectual Property Bureau of the Ministry of Economic Affairs 5 (ppm): -73.8 ( 12F), -80.5 (4F), -118.6 (4F), -123.6 (2F), -187.9 (2F) o [Example 2-3] Manufacturing example of (CF3) 2CFCOF via decomposition reaction of ester bond This paper size In use. National Standard (CNS) A4 (210 > < 297 mm) 〇9- 584628 A7 __B7 V. Description of the invention (37) (Please read the precautions on the back before filling this page) Equipped with a distillation column The distilling route, receiver, and dry ice condensate valve of the Liebich condenser that can be cooled by cold water are prepared in a 20ml reaction container at the top of the reaction container, put into KF (0.7g), and heated at 150 ° C. In the reaction vessel, 9 g of a liquid from which the fluorination reaction product r_i π obtained in Example 7 was removed was gradually added. One hour after the end of the addition, the reaction was completed when no gas was generated. 5.72g of product was recovered in the receiver. The products were FCO (CF0COF (GC area 55%), FC0 (CF2) 3CO0CF2CH (CF3) 2 (GC area 15%), and (CF0CFC0F (GC area 30%)). In the condensate valve, the GC purity was 97% (CF3) 2CFC0F (3.12%) was recovered. [Example 2-4] (CH3) 2CHCH2OH esterification reaction of FC0 (CF2) 2C0F Example 2- Except for changing C0 (CF2) 3C0F and performing FC0 (CF2) 2C0F (950g) in 1, the reaction was performed in the same manner as in 2-1. As a result of GC analysis of the product, 98.8% of (CH3) 2CHCH2 was generated. C〇 (CF2) 2C〇CH2CH (CH3) 2, 1.2% of (CH ^ CHdOCCKCF + COF) did not detect unreacted isobutyl alcohol. This product does not need to be purified and used in the following reactions. Employees, Bureau of Intellectual Property, Ministry of Economic Affairs W-NMRUoodMHz printed by Consumer Cooperative, solvent: CDCh, reference: TMS) 5 (ppm): 0.98 (d, 6H), 2.05 (m, 1H), 4.13 (d, 2H, 19F-NMR (282.7MHz, solvent : CDCh, benchmark: CFCh) 5 (ppm): -120.2 〇 [Example 2-5] (CF3) 2CFCF2 OC (CF2) 2 C 〇CF2CF (CF〇2) produced by the fluorination reaction! 1 The paper size is applicable to Chinese National Standard (CNS) M specifications (210X297 mm) -40-584628 A7 B7 V. Description of the invention (38) A nickel pressure cooker with the same reaction device as in Example 1-2 was prepared. After putting R-113 (312g), 20% diluted fluorine gas was blown in at a flow rate of 12.16L / h. -2 under the same conditions. Into the autoclave, the product (5g) obtained in Example 2-4 was dissolved in R-113 (100g) over 5.7 hours. Continue, while blowing 20% diluted fluorine gas at the same flow rate, increase The internal pressure of the autoclave was 0.15 MPa, and the R-113 solution with a benzene concentration of 0.01 g / mL was injected from 9 ° C to 25 ° C to 40 ° C. The benzene solution injection port of the autoclave was closed, and the stirring was continued for 0.3 hours. The internal pressure of the reactor was maintained at 0.15 MPa, and the temperature of the reactor was maintained at 40 ° C. 6 ml of the benzene solution was injected. The benzene solution injection port of the autoclave was closed, and the stirring was continued for 0.3 hours. The same operation was repeated 3 times. The injection of benzene The total amount was 0 · 2 2 g, and the total injection amount of R -11 3 was 21 m L. Furthermore, while the 20% diluted fluorine gas was blown in at the same flow rate, the stirring was continued for 1.0 hours. The pressure in the reactor was kept constant. Pressure, and nitrogen was blown in for 1.0 hour. 19F-NMR analysis of the product confirmed that the yield of the labeled compound was 90%. 19F-NMR (282.7MHz, solvent: CDCh, reference: CFCl3) 5 (ppm): - 73.8 (12F), - 80,4 (4F), - 119.2 (4F), - 187.8 (2F). [Example 2-6] Production Example of (CF3) 2CFCOF via Decomposition Reaction of Ester Bond The fluorination reaction product of Example 2-3 was changed to the fluorination reaction product obtained in Example 2-5, and slowly added. The same reaction was performed except for the liquid 8.11 lg of R11 3 which was the fluorination reaction product. 1.02g of product recovered in the receiver. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) —-------- installation— (Please read the precautions on the back before filling This page), 11 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -41-584628 A7 B7 V. Invention Description (39) (Please read the precautions on the back before filling this page). The product is FC0 (CF2) 2C0F (GC area 35%), FC0 (CF2) 2C0 CF2CH (CF3) 2 (GC area 60%), (CF3) 2CFC0F (GC area 5%) ). 6.94g was recovered from the gas trap. The product was composed of FC0 (CF2) 2COF (GC area 30%) and (CF3) 2CFCOF (GC area 70%). Industrial Applicability The compound (1) as a raw material of the production method of the present invention is a commercially available product of various compounds having a carbon skeleton, and it can be obtained at low cost. Therefore, the production method of the present invention can freely produce a fluorine-containing compound having a variety of skeletons in a short step and at a high yield from this raw material compound. In addition, by using the method of the present invention, it is possible to easily synthesize a low-molecular fluorinated compound or a fluorinated compound with a complicated structure that was difficult to obtain by conventional methods. In addition, the production method of the present invention is not limited to the compounds described in the above specific examples, but can be applied to a wide variety of other compounds with excellent versatility. In addition, the method of the present invention can be a more industrially applicable and efficient manufacturing method by using a method such as recovery of a compound. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -42- This paper size applies to China National Standard (CNS) A4 (210X297 mm)
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KR100699736B1 (en) * | 1999-03-23 | 2007-03-27 | 아사히 가라스 가부시키가이샤 | Process for producing fluorine compound through liquid-phase fluorination |
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2002
- 2002-06-27 TW TW91114439A patent/TW584628B/en not_active IP Right Cessation
- 2002-06-27 JP JP2003508686A patent/JP4362710B2/en not_active Expired - Fee Related
- 2002-06-27 WO PCT/JP2002/006502 patent/WO2003002501A1/en active Application Filing
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WO2003002501A1 (en) | 2003-01-09 |
JPWO2003002501A1 (en) | 2004-10-14 |
JP4362710B2 (en) | 2009-11-11 |
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