Сообщение
slavert » Вт янв 24, 2006 9:13 pm
А диол известен вот сслыки на диол с иодом и бромом
Bibliographic Information
Glycerol -bromohydrin. Smith, Lennart; Laudon, Johan. Ber. (1933), 66B 899-901. Journal language unavailable. CAN 27:41242 AN 1933:41242 CAPLUS
Abstract
Although there are numerous reports in the literature on the prepn. of "pure" glycerol -bromohydrin (I) it seemed doubtful that the compd. had ever really been prepd. in pure form. This S. and L. have now done by the method used for prepg. the chlorohydrin (removing, from the mixt. of - and -I formed by bromination of allyl alc., the -compd. by repeatedly condensing the mixt. with acetone and distg. off the condensation products; cf. C. A. 25, 3629). The progressive change in the compn. of the distillate and the purity of the final product were controlled by kinetic analysis. From 56.1 g. of a mixt. enriched to a 76% content of -I by 2 condensations with acetone-HBr, there was obtained, by a 3rd condensation with acetone-P2O5, 18.0 g. of a product b6 106 nD18 1.5228, d418 1.7709; the decompn. const. (bimol. reaction) for this product in a Na2CO3-NaHCO3 buffer soln. at 18.0 fell gradually from 8.31 at 21.2% decompn. to 5.19 at 71.2% decompn. Under the same conditions the const. for the -form is about 90; it is difficult to form, from these data, a definite estimate of the degree of purity of the product, but since in the final condensation the product was reduced from 56.1 g. to 18.0 g. and the velocity of condensation of the -form is about 4 times that of the -form, it is calcd. that the final product still contained 2% of the -isomer. The effect of this contamination on the phys. consts. falls within the limits of exptl. error, however.
Indexing -- Section 10 (Organic Chemistry)
3054-01-1, Alanine, -(benzylmercapto)-
4704-87-4, 1,3-Propanediol, 2-bromo-
Bibliographic Information
Conversion of allyl alcohol to glyceryl chloro- and bromohydrins. Read, John; Hurst, Eric. Journal of the Chemical Society, Transactions (1922), 121 989-99. CODEN: JCHTA3 ISSN: 0368-1645. Journal language unavailable. CAN 16:16475 AN 1922:16475 CAPLUS
Abstract
The successful results attending the use of Cl-H2O and Br-H2O in the prepn. of halohydrins from unsatd. substances (C. A. 11, 1952; 14, 2841; 15, 57) led to the application of these reagents to CH2:CH- CH2OH. This gives a mixt. of the -mono- and dihalohydrins. For the prepn. of the -dibalogen deriv., the action of the halogen on CH2: CHCH2OH in CS2 is recommended. The reaction of Br vapors (air satd. with Br) upon CH2: CHCH2OH in H2O at 0-3.5 until the concn. of HOCH2CHBrCH2OH (A) reaches 1 to 1.25 N (as detd. by titration) gives about 60% of the theoretical yield. Its isolation is difficult because it apparently decomps. upon distn. under pressure. 510 g. oil (isolated by satn. of the aq. soln. with Na2SO4 at 30 and extg. 3 times with Et2O), contg. 56% A and 44% BrCH2CHBrCH2OH (B), gave, upon fractional distn. at 20 mm., 55 g. A (20%), b21 136-8, d420 1.7868 (vacuum); its vapor has an irritant action similar to that of BrCH2CH2OH. The yield of B can be practically doubled by using a soln. of CH2:CHCH2OH in its own wt. of H2O; it b20 111-4, d420 2.1197; it is miscible with C6H6 while A is only partly miscible. In the reaction of Cl upon CH2:CHCH2OH in H2O, HOCH2CHClCH2OH © and ClCH2CHClCH2OH (D) are formed, but the yields are low and their sepn. in a state of purity is difficult. This is probably due to the vigor of the reaction and the formation of other products. The yield of C is 10.8%, of D, 11.2% (based on the alc. used). C possesses a marked irritating odor, b13.5 122.5-3.5, d40 1.3416, d420 1.3241 (vacuum). Neither A nor C is completely miscible with H2O. D b13.5 81-1.5, d40 1.3745, d420 1.3534, and is completely miscible with EtOH, Et2O, AcMe and C6H6.
Indexing -- Section 10 (Organic Chemistry)
Carbinols
(dialkylethinyl derivs.)
96-13-9, 1-Propanol, 2,3-dibromo-
497-04-1, 1,3-Propanediol, 2-chloro-
616-23-9, 1-Propanol, 2,3-dichloro-
4704-87-4, 1,3-Propanediol, 2-bromo-
Bibliographic Information
The preparation of glycerol iodides. Bevan, T. H.; Malkin, T.; Smith, D. B. Univ. Bristol, UK. Journal of the Chemical Society, Abstracts (1955), 1383. CODEN: JCSAAZ ISSN: 0590-9791. Journal language unavailable. CAN 50:8121 AN 1956:8121 CAPLUS
Abstract
An O-alkylideneglycerol and (PhO)3P.MeI (I) under anhyd. conditions below 50 gave glycerol iodides which were easily sepd. from the H2O-insol. (PhO)2P-(O)Me (II). Thus, 35 g. 1,2-O-isopropylideneglycerol under anhyd. conditions to 90 g. I with the temp. kept below 50, the oil sepd. after 6 hrs. by shaking the mixt. with 5% NaOH soln. washed with H2O, 5 ml. 5N H2SO4 in 86% EtOH added to the well-drained oil, the mixt. allowed to stand 20 hrs., then refluxed 5 min. to complete hydrolysis, cooled, neutralized with BaCO3, filtered, the filtrate evapd. on a steam bath in vacuo to an oil, the oil extd. several times with H2O to sep. the iodohydrin, NaCl added to the washings, the iodide extd. with Et2O, the ext. dried over Na2SO4, the Et2O distd., and the residual oil crystd. from CHCl3 and then from CHCl3-petr. ether (40-60) gave 29.2 g. glycerol 1-iodide, m. 48.5-9.5; the isopropylidene iodide, b2 70-2, was obtained by dissolving the 1st reaction product in the above process in Et2O, extg. the PhOH and I, drying, distg. the Et2O, and then the product. The by-product II b. 85-90 higher. Glycerol 2-iodide prepd. in a similar manner, using I in a liquid state (yield, 7 g. from 12 g. 1,3-O-benzylideneglycerol), m. 53.
Indexing -- Section 10 (Organic Chemistry)
Thiols
(reactions of, with acetylenic ethers)
56-81-5, Glycerol, iodo compds.
554-10-9, 1,2-Propanediol, 3-iodo-
5349-29-1, 1,3-Propanediol, 2-iodo-
Bibliographic Information
Glycerol - and -monoiodohydrin. Hessel, L. W.; van Lohuizen, O. E.; Verkade, P. E. Tech. Univ., Delft, Neth. Recueil des Travaux Chimiques des Pays-Bas et de la Belgique (1954), 73 842-8. CODEN: RTCPB4 ISSN: 0370-7539. Journal written in English. CAN 49:60226 AN 1955:60226 CAPLUS
Abstract
New methods of prepn. are described for the glycerol monoiodohydrins, m. 48-9 and 53.5-4.5. The latter has become reasonably accessible for the first time. The compd. m. 48-9 is established as the -isomer and that m. 53.5-4.5 the -isomer. Const. boiling HI (133 ml.), distd. over red P in N was added to 74.0 g. glycidol below 10 with stirring during 2 hrs. and H2O and HI were removed in vacuum. The temp. of the bath was raised to 90 under N. Heating was discontinued when the residue suddenly became brown in color. The cooled liquid residue was treated with 2 l. of ether and the extract washed twice with 50 ml. of 0.5N thiosulfate soln., then once with H2O. The three aq. extracts were combined, extd. twice with 200 ml. of Et2O, the combined dry Et2O exts. concd., and the cryst. residue recrystd. 3 times from CHCl3 (5: 1) gave 116.0 g. of the -isomer. Concn. of the combined mother liquors gave another 20.8 g., total yield 68%. The reaction between p-MeC6H4SO2Cl and ,-isopropylideneglycerol in the presence of dry pyridine gave 92% -tosyl-,-isopropylideneglycerol (I), m. 47-8. A soln. of I and NaI in Me2CO refluxed in the dark for 24 hrs. gave -iodo-,-isopropylideneglycerol (II), b1.0 49-50, in 82% yield. II was converted to the -isomer in 81% yield according to Baer and Fischer (C.A. 42, 3322c) with the difference that the aq. H2SO4 soln. was kept only 48 hrs. at 25. Tosyl chloride and ,-benzylideneglycerol, m. 82.5-3.5, in dry pyridine gave 94% -tosyl-,-benzylideneglycerol (III), m. 124.5-5.5. III was hydrogenolyzed in EtAc at 40 over Pd/C catalyst to give -tosylglycerol (IV) as a sirup. A soln. of 12.3 g. of IV and 22.5 g. of NaI in 250 ml. of dry Me2CO was heated to 90-100 in the dark for 5 hrs. The p-MeC6H4SO3Na (9.8 g.) was filtered off. The Me2CO removed in vacuo and to the residue were added 20 ml. of H2O and 250 ml. of Et2O and the mixt. treated with thiosulfate as above, after which the Et2O was removed. The residue was taken up in 40 ml. of 85% alc. contg.
2 ml. of 4N H2SO4 and kept 24 hrs. at 25. The soln. was neutralized with aq. baryta and concd. in vacuo at 40. The resulting sirup was extd. with three 75-ml. portions of Et2O. After drying, the Et2O was removed and the residue crystd. from 20 ml. of CHCl3 to which 10 ml. of petr. ether was added dropwise to give 4.6 g. (HOCH2)2CHI, m. 52-3.5; recrystn. from CHCl3 raised the m.p. to 53.5-4.5.
Indexing -- Section 10 (Organic Chemistry)
7,4-(Epoxymethano)-4H-furo[3,2-d]-m-dioxin, tetrahydro-
56-81-5, Glycerol
(derivs.)
554-10-9, 1,2-Propanediol, 3-iodo-
1708-40-3, 5-m-Dioxanol, 2-phenyl-
5349-29-1, 1,3-Propanediol, 2-iodo-
7305-59-1, 1,3-Dioxolane-4-methanol, 2,2-dimethyl-, p-toluenesulfonate
23737-52-2, 1,3-Dioxolane, 4-(iodomethyl)-2,2-dimethyl-
107274-23-7, 5-m-Dioxanol, 2-phenyl-, p-toluenesulfonate
(prepn. of)
