- Unsaturated nitrogen compounds containing fluorine. Part 12. Reaction of 2--1,1,1,3,3,3-hexafluoropropan-2-ide with monosubstituted ethenes, chlorine and hydrogen chloride
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Treatment of the title azomethinimine (1) with alkenes CH2=CHR (R = CO2H, CHO, OCH3, CH2Br, CH2Cl and OCH2CH2Cl) and dienes CH2=CRCR=CH2 (R = H or Me) results in the regiospecific formation of the 2-substituted cycloadducts in which the CHR group of the alkene is bonded to the nitrogen of the azomethinimine; with isoprene, major addition involves the CH2=CH- grouping.Reaction with chlorine affords a mixture of the dienes (CF3)2C=NNHC(CF3)2CH2CMe=CH2, (CF3)2CClN=NC(CF3)2CH2CMe=CH2 and (CF3)2CClN=NC(CF3)2CH2C(CH2Cl)=CH2, while with hydrogen chloride the diene (CF3)2C=NNHC(CF3)2CH2CMe=CH2 and an adduct, possibly (CF3)2CHN=NC(CF3)2CH2CMe2Cl, are formed.
- Bell, David,Tipping, Anthony E.
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- Method for synthesizing fluoroisobutylene by taking hexafluoropropylene as initial raw material
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The invention discloses a method for synthesizing fluoroisobutylene by taking hexafluoropropylene as an initial raw material. The method comprises the following steps: (1) gas phase addition reaction: in the presence of a block catalyst, hexafluoropropylene and fluoromethane CHFXY (X, Y = F or H) are subjected to gas phase addition to obtain (CF3)2CFCHXY, and (2) dehydrofluorination reaction: in the presence of a dehydrofluorination catalyst, the (CF3)2CFCHXY as a raw material is subjected to dehydrofluorination reaction to obtain (CF3)2C = CXY. The block catalyst and the dehydrofluorination catalyst in the invention have the characteristics of high activity and long service life, and can be used for high-efficiency and gas-phase continuous cycle production of fluoroisobutylene.
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Paragraph 0084
(2021/05/15)
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- Method for continuously preparing 3, 3, 3-trifluoro-2-(trifluoromethyl)-1-propylene in gas phase
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The invention discloses a method for continuously preparing 3, 3, 3-trifluoro-2-(trifluoromethyl)-1-propylene in a gas phase, and the method comprises the following steps: by taking octafluoroisobutylene as a raw material, carrying out hydrogenation-dehydrofluorination-hydrogenation-dehydrofluorination four-step gas phase continuous reaction to obtain the 3, 3, 3-trifluoro-2-(trifluoromethyl)-1-propylene. The hydrogenation catalyst and the dehydrofluorination catalyst have the characteristics of high activity and long service life; according to the present invention, by using the gas phase independent circulation process, the incomplete reaction material is subjected to independent circulation so as to completely convert the initial raw material into the 3, 3, 3-trifluoro-2-(trifluoromethyl)-1-propylene, and finally the product 3, 3, 3-trifluoro-2-(trifluoromethyl)-1-propylene is efficiently and continuously and circularly extracted from the process system in the gas phase; therefore, liquid waste and waste gas are not generated, and green production is realized.
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Paragraph 0085-0099; 0103
(2021/05/15)
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- Preparation method of hexafluoroisobutene
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The invention discloses a preparation method of hexafluoroisobutene. The method comprises the following steps of (a) reacting isobutylene dimethyl ether, benzylhemiformal and halide in an I-type solvent, carrying out rectification to obtain benzopyloxane; (2) reacting the benzopyloxane obtained in the step (1) under the action of a catalyst, filtering and rectifying filtrate to obtain hexafluoro-isobutyrate; (3) reacting the benzopyloxane obtained in the step (1) and a chlorination agent in an II-type solvent, adding water for layering and rectifying an organic layer to obtain hexafluorisobutyrate chloride; and (4) reacting the hexafluorisobutyrate chloride obtained in the step (3) and an organic alkali, condensing and collecting a reaction product to obtain the hexafluoroisobutene. The method has the advantages of being few in three wastes, high in yield, simple in operation and low in cost.
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Paragraph 0042; 0064-0068
(2017/09/01)
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- A six-fluorine different butylene synthetic method (by machine translation)
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The invention discloses a six fluorine different butylene synthetic method, comprises the following steps: (1) will be heptafluoro isobutylene methyl ether and borohydride in the I-type solvent in the reaction, after the reaction filter, and get the hexafluoro-isobutylene methyl ether; (2) the step (1) the obtained hexafluoro-isobutylene methyl ether with acid reaction, after the reaction and get the six fluorine different butyraldehyde; (3) under the action of catalyst, to the step (2) in the butanal obtained six fluorine different hydrogen by the reaction of, after the reaction and filtering to obtain the hexafluoro-isobutyl alcohol; (4) the step (3) the obtained hexafluoro-isobutyl alcohol and alkali reaction in II-type solvent, collecting the reaction product and get the hexafluoro-isobutene product. The invention has simple technique, high yield, the operation is simple, and low cost. (by machine translation)
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Paragraph 0073; 0074; 0075; 0076
(2017/09/02)
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- Preparation method of hexafluoroisobutene
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The invention discloses a preparation method of hexafluoroisobutene, comprising the steps of (1) reacting heptafluoroisobutene methyl ether, methanol and a halide in type I solvent, cooling after reacting, filtering, rectifying the filtrate to obtain methyl hexafluoroisobutyrate; (2) allowing the methyl hexafluoroisobutyrate of step (1) to react with a reducing agent in type II solvent, quenching with hydrochloric acid after reacting, filtering, rectifying the filtrate to obtain hexafluoroisobutanol; (3) allowing the hexafluoroisobutanol of step (2) to react with an alkali in a molar ratio of 1:(1-10) in type III solvent, collecting the reaction product, and rectifying to obtain finished hexafluoroisobutene. The preparation method has the advantages that the process is simple, the yield is high, the raw materials are low in price and easy to obtain and the preparation method is suitable for industrialization.
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Paragraph 0039; 0056-0060
(2017/09/21)
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- The nascent OH detection in photodissociation of 2-(bromomethyl)hexafluoro- 2-propanol at 193 nm: Laser-induced fluorescence study
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Photodissociation of 2-(bromomethyl)hexafluoro-2-propanol (BMHFP) and 3-bromo-1-propanol (BP), involving σC-BrnBr transition at 193 nm, has been investigated by measuring laser-induced fluorescence spectra of the expected OH product. The OH channel is a minor dissociation pathway with a quantum yield of 0.17 ± 0.05 in BMHFP, whereas it was not observed in BP. Partitioning of the available energy into translation, rotation, and vibration of the photoproducts has been measured by state selective detection of the nascent OH product in BMHFP. OH is produced mostly in the ground vibrational level (v″ = 0), with a rotational distribution being characterized by a temperature of 465 ± 25 K. But, a significant fraction of the available energy of 30.2 kcal mol-1 is partitioned into translation of OH (14.6 kcal mol-1). The OH(v″ = 0, J″) populations in the spin-orbit states as well as in the Λ-doublet states are statistical. A plausible mechanism of OH formation on excitation of BMHFP at 193 nm is suggested, with the primary reaction channel being elimination of Br atom by direct C-Br bond dissociation from a repulsive surface. The Br radical is detected using (2 + 1) resonance-enhanced multiphoton ionization (REMPI) at ～234 nm. It is produced in both the ground (2P3/2) and the excited (2P1/2) spin-orbit states with the relative quantum yield of the latter to be 0.36. The co-fragment of Br undergoes secondary C-O bond dissociation to produce OH and F3C-C(CH 2)-CF3, with the reaction having a barrier located in the exit channel. In this two-step three-body dissociation process, a major fraction of the available energy is released into translation (〈fT〉 ～ 0.75), resulting from an impulsive C-Br bond dissociation in the primary step and presence of an exit barrier in the secondary process. Experimental results combined with theoretical calculations provide a clear picture of the dynamics of OH formation from BMHFP at 193 nm. In addition, the energetics of another channel, competing with OH, have been calculated from the primary product F3C-C(CH2)(OH)-CF3. In contrast to BMHFP, the OH product could not be observed from the photolysis of 3-bromo-1-propanol (another saturated halogenated propanol) at 193 nm under the detection limit of the present experimental condition, although it has a higher absorption cross-section at 193 nm.
- Indulkar, Yogesh N.,Upadhyaya, Hari P.,Kumar, Awadhesh,Waghmode, Suresh B.,Naik, Prakash D.
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experimental part
p. 210 - 219
(2012/07/14)
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- Noncatalytic manufacture of 1,1,3,3,3-pentafluoropropene from 1,1,1,3,3,3-hexafluoropropane
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1,1,3,3,3-Pentafluoropropene (CF3CH═CF2, HFC-1225zc) can be produced by pyrolyzing 1,1,1,3,3,3-hexafluoropropane (CF3CH2CF3, HFC-236fa) in the absence of dehydrofluorination catalyst at temperatures of from about 700° C. to about 1000° C. and total pressures of about atmosphere pressure in an empty, tubular reactor, the interior surfaces of which comprise materials of construction resistant to hydrogen fluoride.
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Page/Page column 4
(2008/06/13)
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- Fluorosulfates of hexafluoroisobutylene and its higher homologs
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Hexafluoroisobutylene and its higher homologs are easily reacted with SO3 to give fluorosulfates of the formula CH2═C(R)CF2OSO2F, wherein R is a linear, branched or cyclic fluoroalkyl group comprised of 1 to 10 carbon atoms and may contain ether oxygen. These compounds react under mild conditions with many nucleophiles to give CH2═C(R)CF2X, where X is derived from the nucleophile. This reaction provides a route to many substituted hexafluoroisobutylenes, which copolymerize easily with other fluoro- and hydrocarbon monomers such as vinylidene fluoride and ethylene.
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- PREPARATION OF SELECTED FLUOROOLEFINS
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A process is disclosed for producing (CF3)2C=CH2, CF3CH=CF2, CF2=C(CF3)OCF2CHF2 and C6H5C(CF3)=CF2. The process involves contacting the corresponding fluorocarbon starting material selected from (CF3)2CFCH2F, (CF3)2CHF, (CF3)2CFOCF2CHF2 and C6H5CF(CF3)2, in the vapor phase, with a defluorination reagent selected from carbon, copper, iron, nickel and zinc at an elevated temperature of at least 300 DEG C.
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- Control factors of two reaction modes of pentacoordinate 1,2-oxasiletanides, the peterson reaction and homo-brook rearrangement
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Thermolyses of pentacoordinate 1,2-oxasiletanides with or without a neopentyl group at the 3-position in the presence of a proton source afforded the corresponding olefin and/or alcohol, indicating that they are the intermediates of both the Peterson reaction and homo-Brook rearrangement which are two possible modes in the reaction of β-hydroxyalkylsilanes with bases.
- Naganuma, Kenji,Kawashima, Takayuki,Okazaki, Renji
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p. 1139 - 1140
(2007/10/03)
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- Synthesis of thermolysis of hexacoordinate 1,2-oxaphosphetanides
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β-Hydroxyalkylphosphoranes containing two Martin ligands were prepared by reduction of the corresponding phenylthiomethylphosphorane with lithium naphthalenide, followed by the reaction with carbonyl compounds. Treatment of the β-hydroxyalkylphosphoranes with KH in the presence of 18-crown-6 gave a mixture of stereoisomers of the corresponding hexacoordinate 1,2-oxaphosphetanides stable in solution at room temperature. Upon heating, the adducts of benzophenone derivatives gave the corresponding benzophenones, while a hexafluoroacetone adduct afforded the corresponding olefin.
- Kawashima, Takayuki,Watanabe, Kaoru,Okazaki, Renji
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p. 551 - 554
(2007/10/03)
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- Fluorine-containing compounds, and their preparation and use
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Process for preparing 2-trifluoro-methyl-3,3,3-trifluoropropene.
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- Reaktion von trans-1-Arylbutadienen und 1,1-Diarylbutadienen mit Tetracyanethylen (TCNE) und 2,2-Bis(trifluormethyl)ethylen-1,1-dicarbonitril (BTF): Kinetische Studie
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Kinetic data (substituent effects, solvent effects, activation parameter) are reported for the reactions of trans-1-arylbutadienes 1 and 1,1-diarylbutadienes 3 with TCNE 4 and BTF 5. (2+2)- and (4+2)-cycloadducts 7 respectively 9 can rearrange or undergo cycloreversions with quite different reaction rates depending on the substituent in the aryl-ring.
- Drexler, J.,Lindermayer, R.,Hassan, M. A.,Sauer, J.
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p. 2559 - 2562
(2007/10/02)
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- CONVERSION OF METHOXYPERFLUOROISOBUTENE TO α-METHYLHEXAFLUOROISOBUTYRIC ACID FLUORIDE BY A PHASE TRANSFER CATALYST
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Methoxyperfluoroisobutene was converted to α-methylhexafluoroisobutyric acid fluoride by a catalytic amount of phase transfer catalyst in quantitative yield.
- Misaki, Susumu
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p. 471 - 475
(2007/10/02)
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- Dehydration of 2-Trifluoromethyl-3,3,3-trifluoropropanol with Base
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2-Trifluoromethyl-3,3,3-trifluoropropanol gave 2-trifluoromethyl-3,3,3-trifluoroprop-1-ene in good yield by the action of base under mild conditions.
- Misaki, Susumu,Takamatsu, Shuichi
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p. 531 - 534
(2007/10/02)
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- Preparation of hexafluoroisobutylene
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The process for preparing hexafluoroisobutylene which comprises reacting, at elevated temperatures, ketene or a ketene-generating compound with hexafluorothioacetone. Hexafluoroisobutylene is a known valuable monomer, which forms polymers of exceptional thermal, chemical and mechanical properties, particularly when copolymerized, such as with vinylidene fluoride.
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- Stable fluorinated sulfuranes and sulfurane oxides. Synthesis and reactions
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Bis(trifluoromethyl) sulfide, tetrafluoro-1,3-dithietane, and bis(trifluoromethyl) sulfoxide undergo oxidative addition when photolyzed with trifluoromethyl hypochlorite to form a new family of sulfuranes, bis(trifluoromethyl)bis(trifluoromethoxy)sulfurane (1) and tetrafluoro-1,3-tetrakis(trifluoromethoxy)dithietane (3), and of sulfurane oxides, bis(trifluoromethyl)bis(trifluoromethoxy)sulfurane oxide (2). Compounds 1 and 2 are hydrolyzed to bis(trifluoromethyl) sulfoxide and bis(trifluoromethyl) sulfone, respectively. Pyrolysis of 1, 2, or 3 gives bis(trifluoromethyl) sulfide, bis(trifluoromethyl) sulfoxide, and tetrafluoro-1,3-dithietane, respectively, plus bis(trifluoromethyl) peroxide. With primary amines, 1 and 2 yield N-alkylbis(trifluoromethyl)sulfimides and sulfoxyimides, and with N,N′-diethylaminotrimethylsilane, imine formation occurs. Sulfurane oxide 2 forms a new type of stable sulfurane oxide (4), bis(trifluoromethyl)bis(hexafluoroisopropylidenimido)sulfurane oxide, with lithium hexafluoroisopropylidenimine. Sulfurane 1 acts in a similar manner with the nucleophile but the sulfurane 5 is not isolated. Compounds 1 and 2 form α,α,α-(trifluoromethyl)anisole derivatives with substituted phenols. Secondary and tertiary alcohols are dehydrated by 1 or 2 to olefins but symmetrical alkyl ethers result when primary alcohols are reacted.
- Kitazume, Tomoya,Shreeve, Jean'ne M.
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p. 2173 - 2176
(2007/10/10)
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