Reference_01_08_2014_165529

Reactions of 4-RC6H4CHR1OH (R = H, Me; R1 = CF3, C3F7, CF2CF2OCF3) with (4-R2C6H4O)2POCl (R2 = H, Me) in the presence of CaCl2 or Mg catalyst gave 67-94% 4-RC6H4CHR1OP(O)(OC6H4R2-4)2 (same R-R2).

~4 Citings

Copyright © 2014 American Chemical Society (ACS). All Rights Reserved.

337. Aromatic fluoroalkoxylation via direct displacement of a nitro or fluoro group

By Idoux, John P.; Madenwald, Mark L.; Garcia, Brent S.; Chu, Der Lun; Gupton, John T.

From Journal of Organic Chemistry (1985), 50(11), 1876-8. Language: English, Database: CAPLUS, DOI:10.1021/jo00211a018

Nitroand fluorobenzenes substituted with a range of electron-withdrawing groups readily underwent fluoroalkoxylation via direct displacement of the nitro or fluoro group with CF3CH2ONa. A no. of otherwise inaccessible compds. were synthesized. Yields and reaction conditions were comparable to those reported earlier for reactions involving strong nucleophiles.

~18 Citings

Copyright © 2014 American Chemical Society (ACS). All Rights Reserved.

338. Reaction of trifluoromethylphenylcarbinol with phosphoryl chloride (POCl3), phosphorus pentoxide (P2O5) and on the surface of commercial aluminosilicates

By Gukasyan, A. O.; Shakhnazaryan, G. M.

From Armyanskii Khimicheskii Zhurnal (1983), 36(11), 708-10. Language: Russian, Database: CAPLUS

Reaction of (F3C)PhCHOH (unlike its Cl and Br analogs) with POCl3 gave [(F3C)PhCHO]3PO, (F3C)PhCHOP(O)Cl2 and a diastereomeric mixt. of [(F3C)PhCH]2O (I) whereas with P2O5 and on the surface of silica-alumina at 500°, only I was formed.

~0 Citings

Copyright © 2014 American Chemical Society (ACS). All Rights Reserved.

339. On the relation between elution order and absolute stereochemistry of alkylarylcarbinols from a Pirkle column

By Kasai, Masaji; Froussios, Cleanthis; Ziffer, Herman

From Journal of Organic Chemistry (1983), 48(4), 459-64. Language: English, Database: CAPLUS, DOI:10.1021/jo00152a010

A study of the relation of the abs. stereochem. of alkylarylcarbinols and 2 groups of benzocycloalkenols with their elution order from an HPLC column contg. a chiral stationary phase showed that the enantiomer more strongly retained by the column in each group of compds. has the same abs. stereochem., except for benzoin and its p-Me deriv. The enantiomer more strongly retained in the acyclic series does not have the same abs. stereochem. as that retained in the 2 cyclic series examd. Better sepns. were obsd. in the acyclic series for the acetate esters than the free alcs., while the reverse situation occurred for the benzocycloalkenols. In each series of compds. the enantiomer of the alcs. and corresponding acetates more strongly retained on the column differs in abs. stereochem. These results are not in accord with the current model for chiral recognition on the chiral phase employed. The reliability of using elution order to assign the abs. stereochem. of previously unassigned compds. is compared with other methods currently in use.

~16 Citings

Copyright © 2014 American Chemical Society (ACS). All Rights Reserved.

340. Fluorinated allenes: the syntheses of 1-fluoropropadiene, 1,1-difluoropropadiene and 1,1-difluoro-3-methyl-1,2- butadiene

By Dolbier, William R., Jr.; Burkholder, Conrad R.; Piedrahita, Carlos A.

From Journal of Fluorine Chemistry (1982), 20(5), 637-47. Language: English, Database: CAPLUS, DOI:10.1016/S0022-1139(00)82289-7

Improved synthesis of fluoroallene derivs. (I; R = F, R1 = R2 = H; R = R1 = R2 = H; R = F, R1 = R2 = Me) are presented. Gram quantities of these highly reactive fluorinated allenes may be prepd. conveniently in high purity and up to 97% yield. All 3 are reactive dienophiles and undergo cycloaddn. regiospecifically with cyclopentadiene using their non- fluorine-substituted double bonds to give the corresponding bicycloheptene derivs. (II).

By Zakharov, L. S.; Goryunov, E. I.; Svoren, V. A.; Shcherbina, T. M.; Kabachnik, M. I.

From Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya (1979), (5), 1064-8. Language: Russian, Database: CAPLUS

CF3CHPhOP(O)Cl2 alkylated HCF2CF2ZOH [Z = (CF2)4CH2, CMe2] at 160° to give 46-62% HCF2CF2ZOCHPhCF3. RC6H4CH(CF3)OCHR1CF3 (R = H, R1 = p-tolyl; R = m-CF3, R1 = Ph) were prepd. similarly in 56-9% yields by alkylating RC6H4CH(CF3)OH with CF3CHR1OP(O)Cl2.

~1 Citing

Copyright © 2014 American Chemical Society (ACS). All Rights Reserved.

344. Allylic rearrangements. L. Reactions of α- and γ-trifluoromethylallyl alcohols with thionyl chloride and thermal decomposition of the chlorosulfinate intermediates

By Pegolotti, J. A.; Young, W. G.

From Journal of the American Chemical Society (1961), 83, 3251-8. Language: Unavailable, Database: CAPLUS, DOI:10.1021/ja01476a018

The reactions of α-(trifluoromethyl)allyl alc. (I) and γ-(trifluoromethyl)allyl alc. (II) with SOCl2 in Et2O and SOCl2 were investigated. In the absence of amines, I in either solvent yielded α-(trifluoromethyl)allyl chlorosulfinate (III) only. With I, Bu3N, and SOCl2 (equimolar in ether) the products were 68% III and 32% γ-(trifluoromethyl)allyl chloride (IV) after 1 hr. The presence of Bu3NHCl in the mixt. gave small amts. of IV. II and SOCl2 in ether yielded γ-(trifluoromethyl)allyl chlorosulfinate (V), which slowly gave IV on standing. In the presence of Bu3N, II and SOCl2 gave IV exclusively. III and V, the first isolable allylic chlorosulfinates outside of allyl chlorosulfinate itself, were thermally decompd. with no solvent and in n-decane and nitrobenzene and the rates of decompn. measured by the rate of evolution of SO2 [compd., solvent, decompn, temp., and rate (105k. sec.-1, extrapolated to 100°) given]: III, none (3 runs), 108-110° (103°, 105-106°), 6.5 (6.2, 7.3); III, nitrobenzene, 106-108°, 10.0; III, n-decane, 124°, 1.5; V, none (2 runs), 105° (139-142°), 126 (0.27); V, nitrobenzene (2 runs), 115-116° (118-120°), 5.1 (8.8). The insensitivity of the decompn. to solvent was explained in terms of a concerted reaction with predominant covalent character maintained in the intermediate through the rearrangement sequence. II was prepd. by the procedure of McBee (CA 49, 10171b). I was prepd. by addn. of CF3CHO to the Grignard reagent from vinyl bromide and Mg in tetrahydrofuran; I formed an azeotrope, b. 102-3°, with the solvent. Chromatography of the azeotrope gave I, b. 91.5°, n25 D 1.3450. The α-napthylurethan of I m. 121-3°. Adding 8.9 g. SOCl2 to 9.4 g. II and 13.9 g. Bu3N over 30 min. at 0°, stirring 1 hr., then flash distg. gave IV, b. 82.5-83°, n25 D 1.3610. γ-(Trifluoromethyl)allyl n-amyl sulfite (VI) was prepd. by adding dropwise over 30 min. a mixt. of 3.0 g. II and 1.9 g. anhyd. pyridine to a cooled (-20 to -30°) soln. of 5.12 g. n-amyl chlorosulfinate in ether. H2O was added after 45 min., the layers sepd., the ether layer washed, dried, and distd. to yield 2.05 g. VI, b4 100-102°, n25 D 1.4099. α- (Trifluoromethyl)allyl n-amyl sulfite (VII) was prepd. similarly, b5 80-2°, n25 D 1.4030. Addn. of 4.86 g. SOCl2 in ether to a stirred soln. of 3.57 g. II in 60 ml. ether at 0° and distn. gave 1.23 g. V, b6 55°, n25 D 1.4089. Reaction of V with n-amyl alc. gave VI. Addn. of 3.1 g. I to 14.3 g. SOCl2 and 5.3 g. Bu3N over 45 min. at 0°, with stirring continued 1 hr., and distn. gave 2.78 g. III, b39 52°, n25 D 1.4088. Reaction of III with n-amyl alc. gave VII. The refractive indexes of III and V did not change during 5 min. in the refractometer.

~4 Citings

Copyright © 2014 American Chemical Society (ACS). All Rights Reserved.