The present invention relates to processes for the manufacture of 1,2,3,4-tetrachloro-hexafluoro-butane in a microreactor.

Disclosed is a process for the preparation of cis-1,1,1,4,4,4-hexafluoro-2-butene comprising contacting 1,1,1-trifluorotrichloroethane with hydrogen in the presence of a catalyst comprising ruthenium to produce a product mixture comprising 1316mxx, recovering said 1316mxx as a mixture of Z- and E-isomers, contacting said 1316mxx with hydrogen, in the presence of a catalyst selected from the group consisting of copper on carbon, nickel on carbon, copper and nickel on carbon and copper and palladium on carbon, to produce a second product mixture, comprising E- or Z-CFC-1326mxz, and subjecting said second product mixture to a separation step to provide E- or Z-1326mxz. The E- or Z-1326mxz can be dehydrochlorinated in an aqueous basic solution with an alkali metal hydroxide in the presence of a phase transfer catalyst to produce hexafluoro-2-butyne, which can then be selectively hydrogenated to produce Z-1, 1,1,4,4,4-hexafluoro-2-butene using using either Lindlar's catalyst, or a palladium catalyst further comprising a lantanide element or silver.

Disclosed is a process for the preparation of cis-1,1,1,4,4,4-hexafluoro-2-butene comprising contacting 1,1,1-trifluorotrichloroethane with hydrogen in the presence of a catalyst comprising ruthenium to produce a product mixture comprising 1316mxx, recovering said 1316mxx as a mixture of Z- and E-isomers, contacting said 1316mxx with hydrogen, in the presence of a catalyst selected from the group consisting of copper on carbon, nickel on carbon, copper and nickel on carbon and copper and palladium on carbon, to produce a second product mixture, comprising E- or Z-CFC-1326mxz, and subjecting said second product mixture to a separation step to provide E- or Z-1326mxz. The E- or Z-1326mxz can be dehydrochlorinated in an aqueous basic solution with an alkali metal hydroxide in the presence of a phase transfer catalyst to produce hexafluoro-2-butyne, which can then be selectively hydrogenated to produce Z-1, 1,1,4,4,4-hexafluoro-2-butene using using either Lindlar's catalyst, or a palladium catalyst further comprising a lantanide element or silver.

Disclosed is a process for the preparation of cis-1,1,1,4,4,4-hexafluoro-2-butene comprising contacting 1,1,1-trifluorotrichloroethane with hydrogen in the presence of a catalyst comprising ruthenium to produce a product mixture comprising 1316mxx, recovering said 1316mxx as a mixture of Z- and E-isomers, contacting said 1316mxx with hydrogen, in the presence of a catalyst selected from the group consisting of copper on carbon, nickel on carbon, copper and nickel on carbon and copper and palladium on carbon, to produce a second product mixture, comprising E- or Z-CFC-1326mxz, and subjecting said second product mixture to a separation step to provide E- or Z-1326mxz. The E- or Z-1326mxz can be dehydrochlorinated in an aqueous basic solution with an alkali metal hydroxide in the presence of a phase transfer catalyst to produce hexafluoro-2-butyne, which can then be selectively hydrogenated to produce Z-1, 1,1,4,4,4-hexafluoro-2-butene using using either Lindlar's catalyst, or a palladium catalyst further comprising a lantanide element or silver.

An integrated process for making di-functional or multi-functional molecules with concurrent light paraffin upgrading is disclosed. The process involves three primary steps: (1) oxidation of an iso-paraffin to alkyl hydroperoxide and alcohol; (2) converting the alkyl hydroperoxide and alcohol to dialkyl peroxide; and (3) coupling functional molecules into di-functional or multi-functional molecules using the dialkyl peroxide as a radical initiator, while the dialkyl peroxide is converted to a tertiary alcohol. The functional molecules include any functional molecule RX, where R is a hydrocarbyl group and X is a functional group such as OH, CN, C(O)OH, NH, or the like.

A process for producing E-1,1,1,4,4,4-hexafluorobut-2-ene comprises contacting 1,1,2,4,4-pentachlorobuta-1,3-diene with hydrogen fluoride in the vapor phase in the presence of a fluorination catalyst. A process for producing Z-1,1,1,4,4,4-hexafluorobut-2-ene further comprises contacting E-1,1,1,4,4,4-hexafluoro-2-butene with chlorine in the presence of a catalyst to produce 2,3-dichloro-1,1,1,4,4,4-hexafluorobutane, followed by reaction with base to produce 1,1,1,4,4,4-hexafluoro-2-butyne, and subsequently hydrogenating hexafluoro-2-butyne to produce Z-1,1,1,4,4,4-hexafluoro-2-butene.

A process for producing E-1,1,1,4,4,4-hexafluorobut-2-ene comprises contacting 1,1,2,4,4-pentachlorobuta-1,3-diene with hydrogen fluoride in the vapor phase in the presence of a fluorination catalyst. A process for producing Z-1,1,1,4,4,4-hexafluorobut-2-ene further comprises contacting E-1,1,1,4,4,4-hexafluoro-2-butene with chlorine in the presence of a catalyst to produce 2,3-dichloro-1,1,1,4,4,4-hexafluorobutane, followed by reaction with base to produce 1,1,1,4,4,4-hexafluoro-2-butyne, and subsequently hydrogenating hexafluoro-2-butyne to produce Z-1,1,1,4,4,4-hexafluoro-2-butene.

In the presence of a catalyst and a cycloalkane compound represented by formula (3):

##STR00001##

wherein R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, and R.sup.10 are the same or different and each is a halogen atom, an alkyl group, or a fluoroalkyl group; an alkene compound represented by formula (2):

##STR00002##

wherein X.sup.1, X.sup.2, R.sup.1, and R.sup.2 are as defined above; is reacted with a hydrogen-containing gas to hydrogenate the alkene compound represented by formula (2), whereby an alkane compound represented by R.sup.1CHX.sup.1CHX.sup.2R.sup.2, wherein X.sup.1 and X.sup.2 are the same or different and each is a halogen atom, and R.sup.1 and R.sup.2 are the same or different and each is an alkyl group or a fluoroalkyl group; can be synthesized in such a manner that (S), (R)-isomer, (R), (R)-isomer, and (S), (S)-isomer are co-produced.

In the presence of a catalyst and a cycloalkane compound represented by formula (3):

##STR00001##

wherein R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, and R.sup.10 are the same or different and each is a halogen atom, an alkyl group, or a fluoroalkyl group; an alkene compound represented by formula (2):

##STR00002##

wherein X.sup.1, X.sup.2, R.sup.1, and R.sup.2 are as defined above; is reacted with a hydrogen-containing gas to hydrogenate the alkene compound represented by formula (2), whereby an alkane compound represented by R.sup.1CHX.sup.1CHX.sup.2R.sup.2, wherein X.sup.1 and X.sup.2 are the same or different and each is a halogen atom, and R.sup.1 and R.sup.2 are the same or different and each is an alkyl group or a fluoroalkyl group; can be synthesized in such a manner that (S), (R)-isomer, (R), (R)-isomer, and (S), (S)-isomer are co-produced.

A method for the synthesis of two-dimensional (2D) bismuth (bismuthene) and a use of this material as a photoredox catalyst are provided. The 2D bismuthene is prepared by a liquid-phase exfoliation of the 3D-layered bismuth. The photoredox catalyst is used for the C-H functionalization reactions for the synthesis of complex molecules under versatile conditions.