Bestman, HansJuergen published the artcileReactions with phosphinealkylenes. VII. Olefins and ketones by autoxidation of phosphinealkylenes, Quality Control of 594-81-0, the publication is Chemische Berichte (1963), 96(7), 1899-908, database is CAplus.
cf. CA 58, 13788g. Phosphinealkylenes of the type RCH:PPH3 (R = alkyl) are oxidized by O to olefins and Ph3PO. Phosphinealkylenes of the type RR’C:PPh3 (I) yield with O the corresponding ketones. If the autoxidation of the I is interrupted after consumption of 1 O, olefins can also be formed by the Wittig reaction of the resulting ketone with unoxidized I. Ph3P (26 g.) and 20 g. EtMeCHBr heated 18 hrs. at 100-20° in a sealed tube, and the powd. product boiled 2-3 times with C6H6 yielded 38 g. [iso-BuPPh3]Br (II), m. 235-8° Ph2P (13 g.) and 9.0 g. hexahydrobenzyl bromide heated 24 hrs. at 140-50° in a sealed tube, and the powd. product washed with pert. ether yielded 21 g. triphenylhexahydrobenzylphosphonium bromide (III), m. 225-8° (with softening from 200°). Ph3P (26 g.) and 16 g. p-MeOC6H4CH2Cl heated 1 hr. at 80-100°, and the powd. product boiled 2-3 times with C6H6 yielded 41 g. [p-MeOC6H4CH2PPh3]Cl (IV), m. 214-18° (CHCl3-EtOAc). Ph3P (26 g.) and 27 g. cyclohexyl bromide heated 60 hrs. at 140° in a sealed tube gave similarly 40 g. triphenylcyclohexylphosphonium bromide (V), m. 255-9° (CHCl3-EtOAc). NaNH2 (up to 25% excess) in dry NH3 treated with the dry, powd. phosphonium salt, the NH3 evaporated, the residue boiled about 10 min. with CH6, MePh, Et2O, tetrahydrofuran, etc., and the solution oxidized with O gave the corresponding oxidation products; method A. Na, K, or Li in 100 cc. absolute MeOH, EtOH, or tert-BuOH treated with an equivalent amount dry, powd. phosphonium salt gave a solution of phosphinealkylene which can be oxidized with O; method B. All operations up to the oxidation have to be performed under N or Ar. The oxidations with O were carried out in a special apparatus (described in detail) in which a measured amount O can be recirculated. [PhCH2PPh3]Br (18.0 g.) and 0.92 g. Na in 100 cc. absolute EtOH processed by method B, and the refluxing ylide solution treated 24 hrs. with 0 and poured into 100 cc. 10% HBr precipitated 1.46 g. trans-stilbene (VI), m. 121°; the filtrate evaporated, the residue extracted with Et2O, the extract diluted with petr. ether, the precipitated Ph3PO (10.3 g.) filtered off, and the filtrate distilled gave 0.84 g. cis-stilbene (VII), b12 140-2°, n20D 1.6189. Tricyclohexylbenzylphosphonium chloride (8.1 g.) treated with 0.46 g. Na in 50 cc. absolute EtOH by method B and oxidized 12 hrs. at reflux, and the mixture poured into 50 cc. 10% HBr gave 1.2 g. VI; the acidic mother liquor concentrated gave 1.2 g. unchanged phosphonium salt and 74% tricyclohexylphosphine oxide. [1PhCH2PPh3]Cl treated with 0.6 g. Na and 70 cc. C6H6 by method A, the solution oxidized 5 hrs. at 80° (96% O consumption) and evaporated, and the residue dissolved in 30 cc. MeOH and poured into 20 cc. 10% HBr yielded 1.7 g. VI and only a small amount of VII; the mother liquor diluted with HO precipitated 5.8 g. Ph3PO. IV (12.5 g.), 1.2 g. Na, and 150 cc. dry C6H6 processed by method A, and the solution oxidized 1 hr. at room temperature (84% O consumption) yielded 1.4 g. trans-(MeOCH4CH:)2, m. 210-11° (MeOH-H2O); the mother liquor evaporated and the residue triturated with petr. ether left 6.9 g. Ph3PO; the petr. ether extract distilled yielded 0.70 g. cis-p-(MeOC6H4CH:)2, b0.1 140°, m. 35°. [EtPPh3]Br (11.1 g.) treated by method A with 0.9 g. Na in 150 cc. dry Et2O and oxidized 15 min. at 0% and the effluent gas (swept with N) passed into BrCHCl3 yielded 2.7 g. (MeCHBr)2, b12 58-62°; the Et2O solution yielded 6.2 g. Ph3PO2. [PrPPh3]Br (11.7 g.) treated by method A with 0.9 g. Na and 100 cc. MePh and oxidized 15 min. at 0° (100% O consumption) yielded 0.90 g. 3-hexene, b. 63-5°. [BuPPh3]Br (24 g.) treated with 1.8 g. Na and 150 cc. dry tetrahydrofuran by method A and oxidized 0.5 hr. at room temperature (92% O consumption) gave 14.8 g. Ph3PO and 2.6 g. cis- and trans-4-octene, b710 117-18°; dibromide b10 103°. III (22.0 g.), 1.8 g. Na, and 150 cc. C6H6 processed by method A and oxidized 25 min. at room temperature (100.% O consumption) yielded 11.0 g. Ph3PO, 0.80 g. hexahydrobehzaldehyde, b15 50-3° (2,4-dinitrophenylhydrazone m. 111-13°), and 2.9 g. cis- and trans-1,2-dicyclohexylethylene. [iso-PrPPh3]Br (VIII) (15.8 g.) treated with 0.7 g. Na and 100 cc. MePh by method A and oxidized 5 min. at room temperature (80% O consumption) and the mixture distilled into aqueous 2,4-(O2N)2C6H3NHNH2 gave 2.2 g. 2,4-(O2N)2C6H3NHN:CMe2, m. 126°; the distillation residue evaporated and the residue triturated with 50 cc. petr. ether yielded 2.6 g. Ph3PO. VIII (15.2 g.) treated by method A with 1.3 g. Na in 200 cc. dry C6H6, 1/2 of the resulting solution oxidized with O, the O.removed with N, the remaining unoxidized reaction solution added, the mixture distilled, and the distillate treated with Br yielded 2.8 g. (Me2CBr)2, m. 168-71° (EtOH); the distillation residue gave 6.7 g. Ph3PO. The same result was obtained when the oxidation was interrupted after the consumption of 1 equivalent O and the mixture was kept several hrs.; 53% yield. VIII (6.0 g.) processed with 0.5 g. Na and 100 cc. MePh by method A and oxidized 10 min. at room temperature (75% O consumption), and distilled into aqueous 2,4-(O2N)2C6H3NHNH2.HCl yielded 2.1 g. 2,4-(O2N)2C6H3NHN:CEtMe, m. 116-17°; the residue gave 3.5 g. Ph3PO. VIII (16.0 g.) treated by method A with 1.4 g. Na and 200 cc. dry C6H6, 1/2 of the resulting solution oxidized, purged with N, treated with the remaining unoxidized solution, refluxed under N until pale yellow, and evaporated, and the residue treated with 100 cc. Et2O and cooled gave 9.6 g. Ph3PO; the filtrate distilled yielded 1.3 g. (EtMeC:)2, b. 95-8° [dibromide b760 147-50° (slight decomposition)]; the same results were obtained when the oxidation was interrupted after the consumption of 1 equivalent O; 50% yield. [MePhC:PPh3]Br (8.9 g.) treated with 0.7 g. Na and 100 cc. dry C6H6 by method A and oxidized 15 min. at room temperature (98% O consumption) yielded 4.2 g. Ph3PO; the filtrate evaporated, and the residue treated with EtOH and 2,4-(O2N)2C6H3NHNH2 solution gave 4.1 g. 2,4-(O2N)2C6H3NHN:-CMePh, m. 248°. [Ph2CHPPh3]Br (7.6 g.) treated with 0.6 g. Na and 200 cc. dry C6H6 by method A and oxidized 8 hrs. at room temperature (95% O consumption), the C6H6 distilled, and the residue treated with 60 cc. petr. ether yielded 3.1 g. Ph3PO; the filtrate evaporated and the residue treated with 2,4-(O2N)2C6H3NH-NH2.H3PO4 solution yielded 3.8 g. 2,4-(O2N)2C6H3NHN:CPh2, m. 238°. V (8.5 g.) treated with 0.7 g. Na and 100 cc. C6H6 by method A and oxidized 15 min. at room temperature (77% O consumption), and the mixture worked up in the same manner gave 3.6 g. cyclohexanone 2,4-dinitrophenylhydrazone, m. 158°.
Chemische Berichte published new progress about 594-81-0. 594-81-0 belongs to bromides-buliding-blocks, auxiliary class Bromide,Aliphatic hydrocarbon chain, name is 2,3-Dibromo-2,3-dimethylbutane, and the molecular formula is C6H12Br2, Quality Control of 594-81-0.
Referemce:
https://en.wikipedia.org/wiki/Bromide,
bromide – Wiktionary