GB891178A - Manufacture of olefinically unsaturated compounds - Google Patents
Manufacture of olefinically unsaturated compoundsInfo
- Publication number
- GB891178A GB891178A GB19055/59A GB1905559A GB891178A GB 891178 A GB891178 A GB 891178A GB 19055/59 A GB19055/59 A GB 19055/59A GB 1905559 A GB1905559 A GB 1905559A GB 891178 A GB891178 A GB 891178A
- Authority
- GB
- United Kingdom
- Prior art keywords
- phosphine oxide
- diphenyl
- benzophenone
- benzaldehyde
- methyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
- C07C1/324—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom the hetero-atom being a phosphorus atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Olefinically unsaturated compounds are prepared by condensation of a carbonyl compound and a phosphine oxide or phosphonate in the presence of a metal alcoholate according to the equation <FORM:0891178/IV (b)/1> wherein: R1 is alkyl, alkenyl, aralkyl, aralkenyl, aryl or heterocyclic; R2 is hydrogen, alkyl, alkenyl, aralkyl, aralkenyl, aryl or heterocyclic or is acyl, in which case condensation also occurs at the second carbonyl group, or R1 and R2 together with the carbonyl group form a five- or six-membered ring system; R3 is alkyl, alkyloxy, aryl or aryloxy; R4 is alkyl, alkyloxy, aralkyl, aralkyloxy, aryl or aryloxy; R5 is hydrogen, alkyl, alkenyl, aralkyl or aryl; R6 is hydrogen, alkyl or aryl provided that R3, R4, R5 and R6 do not all represent ary groups. Usually equivalent proportions of the reactants are reacted in an inert solvent such as benzene, toluene, xylene, cyclohexane, anisol or benzonitrile, at 50 DEG C.-150 DEG C. The sodium or potassium alcoholates especially of secondary and tertiary alcohols are preferred, e.g., sodium ethylate, propylate isobutylate or benzylate or potassium tert.-butylate or tert.-amylate. The examples refer to condensations between (1) diphenyl benzyl phosphine oxide and benzophenone to form triphenylethylene; (2) diphenyl methyl phosphine oxide and benzophenone to form 1 : 1-diphenylethylene; (3) diphenyl ethyl phosphine oxide and benzophenone to form diphenylpropene; (4) diphenyl butyl phosphine oxide and benzophenone to form diphenylpentene; (5) diphenyl benzyl phosphine oxide and acetophenone to form a -methyl stilbene; (6) diphenyl benzyl phosphine oxide and benzaldehyde to form stilbene; (7) diphenyl benzyl phosphine oxide and cyclohexanone to form benzylidene cyclohexane; (8) diphenyl benzyl phosphine oxide and cinnamic aldehyde to form 1 : 4-diphenyl butadiene; (9) diphenyl benzyl phosphine oxide and fluorenone to form benzalfluorene; (10) diphenyl benzyl phosphine oxide and methyl ethyl ketone to form 1-methyl-1-ethyl styrene; (11) diphenyl benzyl phosphine oxide and benzil to form 1,2,3,4-tetraphenyl butadiene; (12) diphenyl benzyl phosphine oxide and terephthalaldehyde to form distyryl benzene; (13) diphenyl benzyl phosphine oxide and pyridine-3-aldehyde to form b -stilbazole; (14) diphenyl benzyl phosphine oxide and pyridine-4-aldehyde to form g -stilbazole; (15) diphenyl allyl phosphine oxide and benzophenone to form 1 : 1-diphenylbutadiene; (16) diphenyl-1-phenylethyl phosphine oxide and benzaldehyde to form a -methylstilbene; (17) diphenyl benzyl phosphine oxide and methyl isopropyl ketone to form 1-methyl-1-isopropyl styrene; (18) diphenyl butyl phosphine oxide and benzophenone to form 1 : 1-diphenyl-2-propyl ethylene and diphenyl benzyl phosphine oxide and benzaldehyde to form 1 : 2-diphenyl ethylene; (19) diethyl benzylphosphonate and benzophenone to form triphenylethylene; (20) dibutyl benzylphosphonate and benzaldehyde to form stilbene; (21) diethyl butylphosphonate and benzophenone to form diphenylpentane; (22) diethyl butylphosphonate and benzaldehyde to form phenylpentene; (23) diethyl 1-phenylethylphosphonate and benzaldehyde to form a -methyl stilbene; (24) diethyl o -carbomethoxy allyl-phosphonate and benzaldehyde to form, after hydrolysis, cinnamyl acetic acid. The phosphinic acid or phosphonic acid ester also formed may be recovered and the phosphinic acid reconverted to the phosphine oxide by a Grignard reagent by way of the chloride.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE891178X | 1958-06-03 |
Publications (1)
Publication Number | Publication Date |
---|---|
GB891178A true GB891178A (en) | 1962-03-14 |
Family
ID=6843408
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB19055/59A Expired GB891178A (en) | 1958-06-03 | 1959-06-03 | Manufacture of olefinically unsaturated compounds |
Country Status (1)
Country | Link |
---|---|
GB (1) | GB891178A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0018532A1 (en) * | 1979-04-23 | 1980-11-12 | Bayer Ag | 1-Aryl-4-methyl-penta-1,2-dienes, process for their preparation and their use for the preparation of 3-(2-aryl-vinyl)-2,2-dimethylcyclopropane-1-carboxylates |
WO2001060774A1 (en) * | 2000-02-16 | 2001-08-23 | Brigham Young University | Synthesis of resveratrol |
-
1959
- 1959-06-03 GB GB19055/59A patent/GB891178A/en not_active Expired
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0018532A1 (en) * | 1979-04-23 | 1980-11-12 | Bayer Ag | 1-Aryl-4-methyl-penta-1,2-dienes, process for their preparation and their use for the preparation of 3-(2-aryl-vinyl)-2,2-dimethylcyclopropane-1-carboxylates |
WO2001060774A1 (en) * | 2000-02-16 | 2001-08-23 | Brigham Young University | Synthesis of resveratrol |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US2579810A (en) | Process of preparing substituted hydroxymethylphosphonic esters | |
Ramaiah | Cyclopentaannellation reactions in organic synthesis | |
Nozaki et al. | Trialkylborane as an initiator and terminator of free radical reactions. Facile routes to boron enolates via. ALPHA.-carbonyl radicals and aldol reaction of boron enolates. | |
Wadsworth et al. | The utility of phosphonate carbanions in olefin synthesis | |
CA1045144A (en) | Ethers | |
Sekine et al. | Silyl phosphites. XVIII. Versatile utility of. ALPHA.-(trimethylsilyloxy)-alkylphosphonates as key intermediates for transformation of aldehydes into several carbonyl derivatives. | |
Aso et al. | Simple titration method using diphenyl ditelluride as a colored indicator for the determination of organolithium and organomagnesium reagents | |
GB1307315A (en) | Fire retardant polyurethanes | |
Akermark et al. | Addition of ketone enolates to π-allylpalladlum compounds. Stereochemistry and scope of the reaction | |
GB891178A (en) | Manufacture of olefinically unsaturated compounds | |
US3277217A (en) | Process for producing phosphate esters by oxidation of phosphites using hydrogen peroxide and organic peroxides as catalyst | |
Cast et al. | 706. Molecular rearrangement and fission of ethers by alkaline reagents | |
Ishikawa et al. | Reaction of acetals with Grignard reagents. | |
Trippett et al. | 405. The use, in Wittig reactions, of phosphonium salts and phosphobetaines containing a basic group | |
Baba | The Reaction of Triethylaluminum with Esters | |
US3308172A (en) | Asymmetric synthesis of alcohols | |
US3117165A (en) | Substituted tertiary phosphine oxides | |
Sekine et al. | A new type of P-C and C-C bond cleavage reactions in. ALPHA.-trimethyl-silyloxy-. BETA.-oxo phosphonates and. ALPHA.-ethoxy-. BETA.-oxo phosphonates. The synthesis of unsymmetrical. ALPHA.-hydroxy ketones utilizing 1: 1 carbonyl adducts of diethyl trimethylsilyl phosphite with benzaldehyde. | |
US3576889A (en) | Ethynylation of ketones and aldehydes to obtain alcohols | |
US2954402A (en) | Method of producing substituted borazoles | |
US3116334A (en) | Novel phosphine oxides and methods of preparing same | |
US2824139A (en) | Fluorochloro ketones and methods for the preparation thereof | |
GB930522A (en) | Manufacture of olefinic compounds | |
US3104264A (en) | Manufacture of diarylalkyl phosphine oxides | |
Hayes et al. | Carbanion rearrangements: Collisionally activated dissociations of deprotonated alkyl malonates |