GB1575236A - Fluorine substituted trihydrocarbyl phosphites arsenites and antimonites - Google Patents

Fluorine substituted trihydrocarbyl phosphites arsenites and antimonites Download PDF

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GB1575236A
GB1575236A GB1275879A GB1275879A GB1575236A GB 1575236 A GB1575236 A GB 1575236A GB 1275879 A GB1275879 A GB 1275879A GB 1275879 A GB1275879 A GB 1275879A GB 1575236 A GB1575236 A GB 1575236A
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trifluoro
phosphite
substituted
trifluoromethyl
ethyl
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/141—Esters of phosphorous acids
    • C07F9/1414—Esters of phosphorous acids with arylalkanols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/141—Esters of phosphorous acids
    • C07F9/145—Esters of phosphorous acids with hydroxyaryl compounds

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)

Description

(54) FLUORINE SUBSTITUTED TRIHYDROCARBYL PHOSPHITES, ARSE NITES AND ANTIMONITES (71) We. SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V., a company organised under the laws of The Netherlands of 30 Carel van Bylandtlaan, The Hague, The Netherlands. do hereby declare the invention. for which we pray that a patent may be granted to us. and the method by which it is to be performed, to be particularly described in and by the following statement: The invention relates to novel esters and to a process for the preparation of these novel esters.
The novel esters of the present invention are substituted trihydrocarbyl phosphites, substituted trihydrocarbyl arsenites and substituted trihydrocarbyl antimonites, wherein at least one of the three hdrocarbyl groups is a substituted hydrocarbyl group of the general formula CF3-(CF2)n-C(H)(R)- (I) wherein n is equal to zero or an integer of at least one and R represents a substituted or unsubstituted hydrocarbyl group. with the proviso that not all three hydrocarbyl groups in the substituted trihydrocarbyl phosphites are equal substituted hydrocarbyl groups of formula I with the exception that all three hydrocarbyl groups may be 2.2.2-tnfluoro-1-phenylethyl groups.
The novel esters are particularly useful for preparing catalysts by the mixing thereof with a compound of a metal of Group VIII of the Periodic Table of the Elements, e.g. nickel. in which the metal has an oxidation number of zero. Such catalysts are particularly useful in processes for preparing 1.5-dimethyl-l .5-cyclooctadiene and 1.4-dimethyl-4-vinyl-l cvclohexene from isoprene. Such catalysts and processes are claimed and described in our do-pending Application No. 02100/77. (Serial No. 1575235).
The hydrocarbyl group represented by R in formula 1 may be, for example. an alkyl. a cycloalkyl or an arvl group. Examples of these hydrocarbyl groups are methyl, ethyl. propyl.
isopropyl. cyclohexyl and phenyl groups. Each of these hydrocarbyl groups may be substituted. Examples of substituents are fluorine. chlorine and bromine atoms and alkoxy and phenoxy groups.
Suitable esters are those in which at least two trifluoromethyl groups in the substituted tri hydrocarbyl phosphite. substituted trilydrocarbvl arsenite or substituted trihydrocarbyl antimonite are bound to one or two H - C - groups one of which is shown in formula I. The latter group is. of course. also bound to an oxygen atom of the phosphite. arsenite or antimonite. Examples of such substituted trihydrocarbyl phosphites are di(2.2.2-trifluoro-l-phenylethyl) phenyl phosphite.
di(2 .2 .2-trifluoro-l-phenylethyl methyl phosphite.
di(2.2.2-trifluoro-l-phenylethxl) isopropyl phosphite. and diphenyl 2.2.2-tri-fluoro-l-(trifluoromethyl) ethyl phosphite.
Preferred esters are those in which at least three trinuoromethyl groups in the substituted trihydrocarbyl phosphite. substituted trihydrocarbyl arsenite or substituted trihydrocarbyl antimonite are bound to - C, - H groups. one of which is shown in formula I. Examples of such substituted trihydrocarbyl phosphites are phenyl 2,2,2-trifluoro-l-phenylethyl 2,2,2-trifluoro-l-(trifluoromethyl) ethyl phosphite, isoprbpyl 2,2,2-trifluoro-l-phenylethyl 2,2,2-trifluoro-l-(trifluoro-methyl) ethyl phosphite, 2 ,2,2-trifluoro-l-methylethyl di(2,2,2-trifluoro-l-phenylethyl) phosphite, and tri(2,2,2- trifluoro-l-phenylethyl) phosphite.
More preferred esters are those in which at least four trifluoromethyl groups in the substituted trihydrocarbyl phosphite, substituted trihydrocarbyl arsenite or substituted trihydrocarbyl antimonite are bound to - C - H groups, one of which is shown in formula I.
Examples of such substituted trihydrocarbyl phosphites are di(2,2,2-trifluoro-l-phenylethyl) 2,2,2-trifluoro-l-(trifluoromethyl) ethyl phosphite, 2,2,2-trifluoro-l-methylethyl 2,2 ,2-trifluoro-l-phenylethyl 2,2,2-trifluoro-l-(trifluoromethyl) ethyl phosphite, methyl di t2,2,2-trifluoro-l-(trifluoromethyl)ethyl] phosphite, and phenyl di[2,2,2trifluoro-l-(trifluoromethyl)ethyl] phosphite.
Most preferred esters are those in which at least five trifluoromethyl groups in the substituted trihydrocarbyl phosphite, substituted trihydrocarbyl arsenite or substituted trihydrocarbyl antimonite are bound to - ( - H groups, one of which is shown in formula I.
Examples of such substituted trihydrocarbyl phosphites are 2,2,2-trifluoro-l-phenylethyl di[2,2,2-trifluoro-l-(trifluoromethyl) ethyl phosphite, and 2,2,2-trifluoro-l-methylethyl di2,2,2-trifluoro-l-trifluoromethyl) ethyl] phosphite.
The novel substituted trihydrocarbyl phosphites, substituted trihydrocarbyl arsenites and substituted trihydrocarbyl antimonites may be prepared by reacting an alcohol of the general formula CF3 - (CF2)n - C(H)(R)OH (11) wherein n and R have the same meaning as in formula I, with a compound of the general formula Z(R 1)(R2)(R3) (III) wherein each of the symbols Rt, R2 and R3 represents a halogen atom or a substituted or unsubstituted hydrocarbyloxy group and Z a phosphorus, arsenic or antimony atom; in the presence of an acid acceptor.
The Examples further illustrate the invention.
Example I - Preparation of phenyl di [2,2,2-trifluoro-l-(trifluoromethyl) ethyl] phosphite A mixture of 6 mol of phosphorus trichloride and 1 mol of phenol was heated under reflux for four hours. The reaction mixture thus formed was distilled to isolate the phenyl dichlorophosphite - PC12(OC6H5) - formed. A freshly distilled amount of 59 mmol of phenyl dichlorophosphite was stirred into 50 ml of diethyl ether and after the temperature had been lowered to -20"C, a solution of 12.2 ml of 1,1,1,3,3,3-hexafluoro-2-propanol and 9.5 ml of pyridine in 150 ml of diethyl ether was added. The mixture thus formed was allowed to adopt a temperature of 22"C while being stirred and kept overnight at this temperature. The precipitate formed was filtered off, the solvent was evaporated from the filtrate giving a residue which was distilled at sub-atmospheric pressure to isolate the title compound in a yield of 20%, calculated on starting phenyl dichlorophosphite. The title compound had a boiling point of 110 C at 20 mmHg.
Example II - Preparation of tri(2,2,2-trifluoro-l-phenylethyl) phosphite A solution of 57 mmol of phosphorus trichloride in 25 ml of diethyl ether was added dropwise at a temperature of -10 C to a solution of 170 mmol of 2,2,2-trifluoro-lphenylethanol and 170 mmol of pyridine in 100 ml of diethyl ether. The mixture thus formed was allowed to adopt a temperature of 22"C while being stirred and kept overnight at this temperature. The precipitate formed in the mixture was filtered off, the solvent was evaporated from the filtrate giving a residue which was distilled at sub-atmospheric pressure to isolate the title compound in a yield of 95 %, calculated on starting phosphorus trichloride.
The title compound boiled between 150 and 154"C at 0.1 mmHg.
Example Ill - Preparation of diphenyl 2,2,2-trifluoro-1-(trifluoromethyl) ethyl phosphite An amount of 28.2 mmol of 1,1,1,3,3,3-hexafluoro-2-propanol together with 0.1 mmol of solid sodium hydroxide was added to 84.6 mmol of triphenyl phosphite at a temperature of 22"C. The mixture thus formed was stirred for one hour and then heated under reflux for another hour. Then the solvent was evaporated from the mixture, giving a residue which was distilled at sub-atmospheric pressure to isolate the title compound in a yield of 18.5%, calculated on starting 1,1,1,3,3 ,3-hexafluoro-2-propanol.
WHAT WE CLAIM IS: 1. Substituted trihydrocarbyl phosphites, substituted trihydrocarbyl arsenites and substituted trihydrocarbyl antimonites, wherein at least one of the three hydrocarbyl groups is a substituted hydrocarbyl group of the general formula CF3 - (CF2)n - C(H)(R) - (I) wherein n is equal to zero or an integer of at least one and R represents a substituted or unsubstituted hydrocarbyl group, with the proviso that not all three hydrocarbyl groups in the
**WARNING** end of DESC field may overlap start of CLMS **.

Claims (6)

**WARNING** start of CLMS field may overlap end of DESC **. phenyl 2,2,2-trifluoro-l-phenylethyl 2,2,2-trifluoro-l-(trifluoromethyl) ethyl phosphite, isoprbpyl 2,2,2-trifluoro-l-phenylethyl 2,2,2-trifluoro-l-(trifluoro-methyl) ethyl phosphite, 2 ,2,2-trifluoro-l-methylethyl di(2,2,2-trifluoro-l-phenylethyl) phosphite, and tri(2,2,2- trifluoro-l-phenylethyl) phosphite. More preferred esters are those in which at least four trifluoromethyl groups in the substituted trihydrocarbyl phosphite, substituted trihydrocarbyl arsenite or substituted trihydrocarbyl antimonite are bound to - C - H groups, one of which is shown in formula I. Examples of such substituted trihydrocarbyl phosphites are di(2,2,2-trifluoro-l-phenylethyl) 2,2,2-trifluoro-l-(trifluoromethyl) ethyl phosphite, 2,2,2-trifluoro-l-methylethyl 2,2 ,2-trifluoro-l-phenylethyl 2,2,2-trifluoro-l-(trifluoromethyl) ethyl phosphite, methyl di t2,2,2-trifluoro-l-(trifluoromethyl)ethyl] phosphite, and phenyl di[2,2,2trifluoro-l-(trifluoromethyl)ethyl] phosphite. Most preferred esters are those in which at least five trifluoromethyl groups in the substituted trihydrocarbyl phosphite, substituted trihydrocarbyl arsenite or substituted trihydrocarbyl antimonite are bound to - ( - H groups, one of which is shown in formula I. Examples of such substituted trihydrocarbyl phosphites are 2,2,2-trifluoro-l-phenylethyl di[2,2,2-trifluoro-l-(trifluoromethyl) ethyl phosphite, and 2,2,2-trifluoro-l-methylethyl di2,2,2-trifluoro-l-trifluoromethyl) ethyl] phosphite. The novel substituted trihydrocarbyl phosphites, substituted trihydrocarbyl arsenites and substituted trihydrocarbyl antimonites may be prepared by reacting an alcohol of the general formula CF3 - (CF2)n - C(H)(R)OH (11) wherein n and R have the same meaning as in formula I, with a compound of the general formula Z(R 1)(R2)(R3) (III) wherein each of the symbols Rt, R2 and R3 represents a halogen atom or a substituted or unsubstituted hydrocarbyloxy group and Z a phosphorus, arsenic or antimony atom; in the presence of an acid acceptor. The Examples further illustrate the invention. Example I - Preparation of phenyl di [2,2,2-trifluoro-l-(trifluoromethyl) ethyl] phosphite A mixture of 6 mol of phosphorus trichloride and 1 mol of phenol was heated under reflux for four hours. The reaction mixture thus formed was distilled to isolate the phenyl dichlorophosphite - PC12(OC6H5) - formed. A freshly distilled amount of 59 mmol of phenyl dichlorophosphite was stirred into 50 ml of diethyl ether and after the temperature had been lowered to -20"C, a solution of 12.2 ml of 1,1,1,3,3,3-hexafluoro-2-propanol and 9.5 ml of pyridine in 150 ml of diethyl ether was added. The mixture thus formed was allowed to adopt a temperature of 22"C while being stirred and kept overnight at this temperature. The precipitate formed was filtered off, the solvent was evaporated from the filtrate giving a residue which was distilled at sub-atmospheric pressure to isolate the title compound in a yield of 20%, calculated on starting phenyl dichlorophosphite. The title compound had a boiling point of 110 C at 20 mmHg. Example II - Preparation of tri(2,2,2-trifluoro-l-phenylethyl) phosphite A solution of 57 mmol of phosphorus trichloride in 25 ml of diethyl ether was added dropwise at a temperature of -10 C to a solution of 170 mmol of 2,2,2-trifluoro-lphenylethanol and 170 mmol of pyridine in 100 ml of diethyl ether. The mixture thus formed was allowed to adopt a temperature of 22"C while being stirred and kept overnight at this temperature. The precipitate formed in the mixture was filtered off, the solvent was evaporated from the filtrate giving a residue which was distilled at sub-atmospheric pressure to isolate the title compound in a yield of 95 %, calculated on starting phosphorus trichloride. The title compound boiled between 150 and 154"C at 0.1 mmHg. Example Ill - Preparation of diphenyl 2,2,2-trifluoro-1-(trifluoromethyl) ethyl phosphite An amount of 28.2 mmol of 1,1,1,3,3,3-hexafluoro-2-propanol together with 0.1 mmol of solid sodium hydroxide was added to 84.6 mmol of triphenyl phosphite at a temperature of 22"C. The mixture thus formed was stirred for one hour and then heated under reflux for another hour. Then the solvent was evaporated from the mixture, giving a residue which was distilled at sub-atmospheric pressure to isolate the title compound in a yield of 18.5%, calculated on starting 1,1,1,3,3 ,3-hexafluoro-2-propanol. WHAT WE CLAIM IS:
1. Substituted trihydrocarbyl phosphites, substituted trihydrocarbyl arsenites and substituted trihydrocarbyl antimonites, wherein at least one of the three hydrocarbyl groups is a substituted hydrocarbyl group of the general formula CF3 - (CF2)n - C(H)(R) - (I) wherein n is equal to zero or an integer of at least one and R represents a substituted or unsubstituted hydrocarbyl group, with the proviso that not all three hydrocarbyl groups in the
substituted trihydrocarbyl phosphites are equal substituted hydrocarbyl groups of formula I with the exception that all three hydrocarbyl groups may be 2,2,2-trifluoro-l-phenylethyl groups.
2. Diphenyl 2,2,2-trifluoro-l-(trifluoromethyl)ethyl phosphite.
3. Tri(2,2,2-trifluoro-l-phenylethyl) phosphite.
4. Phenyl di[2,2,2-trifluoro-l-(trifluoromethyl)ethyl]phosphite.
5. Process for the preparation of a substituted trihydrocarbyl phosphite, substituted trihydrocarbyl arsenite or substituted trihydrocarbyl antimonite as claimed in claim 1, which comprises reacting an alcohol of the general formula CF3 - (CF2)n - C(H)(R)OH (11) wherein n and R have the same meaning as in formula I of claim 1, with a compound of the general formula Z(R1)(R2)(R3) (III) wherein each of the symbols Rì, R2 and R3 represents a halogen atom or a substituted or unsubstituted hydrocarbyloxy group and Z a phosphorus, arsenic or antimony atom, in the presence of an acid acceptor.
6. Process as claimed in claim 5, substantially as hereinbefore described with reference to any of Examples I-III.
A > aet rot t1 o A nto fo
GB1275879A 1978-01-17 1978-01-17 Fluorine substituted trihydrocarbyl phosphites arsenites and antimonites Expired GB1575236A (en)

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