Reductive dehalogenation of polyhalofluorocarbons with tributyltin hydride
作者:Michael Van Der Puy、Randolph K. Belter、Ralph J. Borowski、Lois A.S. Ellis、Phillip J. Persichini、Andrew J. Poss、Theodore P. Rygas、Harry S. Tung
DOI:10.1016/0022-1139(94)03153-q
日期:1995.3
The reduction of polyhalofluorocarbons, including ClCF2CFClCF2Cl, (ClCF2CFCl)2, ICH2(CF2)3CH2I and vicinal dichloro-perfluorocycloalkanes, with tributyltinhydride gave the corresponding hydrofluorocarbons in good to excellent yield. The results are compared with similar reductions with other reducing agents, and to tin hydridereductions of non-fluorinated analogs.
A process for preparing (per)fluorohalogenethers having general formula (I):
(R)
n
C(F)
m
OCAF—CA′F
2
(I)
wherein:
A and A′, equal to or different the one from the other, are Cl or Br or one is selected from A and A′ and hydrogen and the other is halogen selected from Cl, Br; R═F, or a fluorinated, preferably perfluorinated, substituent, selected from the following groups: linear or branched C
1
-C
20
alkyl more preferably C
1
-C
10
; C
3
-C
7
cycloalkyl; aromatic, C
6
-C
10
arylalkyl, alkylaryl; C
5
-C
10
heterocyclic or alkylheterocyclic; when R is fluorinated or perfluorinated alkyl, cycloalkyl, arylalkyl, alkylaryl, it can optionally contain in the chain one or more oxygen atoms;
when R is fluorinated it can optionally contain one or more H atoms and/or one or more halogen atoms different from F: n is an integer and is 1 or 2; m=3-n;
by reaction of carbonyl compounds having formula (II):
(R)
p
C(F)
q
(O) (II)
wherein:
p is an integer and is 1 or 2; q is an integer and is zero or 1, R is as above;
in liquid phase with elemental fluorine and with olefinic compounds having formula (III):
CAF═CA′F (III)
wherein A and A′ are as above, at temperatures in the range from −120° C. to −20° C.
[EN] PROCESS FOR THE SYNTHESIS OF PERFLUOROBUTADIENE<br/>[FR] PROCÉDÉ DE SYNTHÈSE DE PERFLUOROBUTADIÈNE
申请人:SOLVAY SOLEXIS SPA
公开号:WO2009087067A1
公开(公告)日:2009-07-16
Process for preparing perfluoro-1,3-butadiene, comprising the following steps : A) preparation of fluoro-halo-butanes of formula : CF2 YI -CFYIICFYIICF2 YI (V) in which YI and YII which may be identical or different, may be H, C1 or Br, with the condition that YI and YII are not simultaneously hydrogen; starting with a chloroolefin having the formula : CY'Y = CY'C1 (II) in which Y, Y', Y', which may be identical or different, are H, C1 or Br, with the condition that Y, Y', Y' are not simultaneously hydrogen; and performing the following steps : - a fluorodimerization, and - a fluorination with elemental fluorine, the order of the two steps also possibly being inverted, - a dehalogenation or dehydrohalogenation step being performed between the two steps, B) dehalogenation or dehydrohalogenation of the fluoro-halo compounds of formula (V) to give the compound perfluoro-1,3-butadiene.
制备全氟-1,3-丁二烯的过程,包括以下步骤:A)制备具有以下结构的氟-卤代丁烷:CF2 YI -CFYIICFYIICF2 YI(V),其中YI和YII可能相同或不同,可以是H、Cl或Br,条件是YI和YII不能同时为氢;从具有以下结构的氯烯烃开始:CY'Y = CY'C1(II),其中Y、Y'、Y'可能相同或不同,可以是H、Cl或Br,条件是Y、Y'、Y'不能同时为氢;并执行以下步骤:- 氟二聚化,- 用元素氟进行氟化,两个步骤的顺序也可能被颠倒,- 在两个步骤之间执行去卤或去卤氢化步骤,B)对具有结构式(V)的氟-卤化合物进行去卤或去卤氢化,得到化合物全氟-1,3-丁二烯。