Chromium II chloride

The anhydrous hahdes, chromium (II) fluoride [10049-10-2], chromium (II) bromide [10049-25-9], CrBr2, chromium (II) chloride [10049-05-5], CrCl2, and chromium (II) iodide [13478-28-9], 03x1, are prepared by reaction of the hydrohaUde and pure Cr metal at high temperatures, or anhydrous chromium (II) acetate [15020-15-2], Cr2(CH2COO)4, atlower temperatures, or by hydrogen reduction of the Cr(III) hahde at about 500—800°C (2,12). 

Chromium (II) chloride (anhydrous) [10049-05-5] M 122.9, m 824 , d]" 2.75, Obtained from the dihydrate by heating in vacuo at 180°. It is a very hygroscopic white powder which dissolves in H2O to give a sky blue solution. Stable in dry air but oxidises rapidly in moist air and should be stored in air tight containers. It sublimes at 800° in a current of HCl gas and cooled in the presence of HCl gas. Alternatively it can be washed with air-free Et20 and dried at 110-120°. [Inorg Synth 3 150 1950.]... 

Chrom-bleii n. lead chromate, -bleispat, m. (Min.) crocoite. -braun, n. chrome brown, -chlorid, n. chromic chloride. chromium(III) chloride, -chlorilr, n, chromous chloride, chromium(II) chloride, -druck, m. (Calico) chrome printing. 

Chromo-. chromous, chromium(II). -chlorid, n. chromous chloride, chromium(II) chloride. 

The Ni(ii)/Cr(n)-mediated coupling reaction employs an excess of chromium(ii) chloride and a catalytic amount of nickel(n) chloride (0.1 %). The preferred solvent for this reaction is usually DMF, although THF, DMF/THF, or DMF/Me2S may also be used. The ability to activate the vinyl iodide (or related) substrate at ambient... 

It is possible to titrate two substances by the same titrant provided that the standard potentials of the substances being titrated, and their oxidation or reduction products, differ by about 0.2 V. Stepwise titration curves are obtained in the titration of mixtures or of substances having several oxidation states. Thus the titration of a solution containing Cr(VI), Fe(III) and V(V) by an acid titanium(III) chloride solution is an example of such a mixture in the first step Cr(VI) is reduced to Cr(III) and V(V) to V(IV) in the second step Fe(III) is reduced to Fe(II) in the third step V(IV) is reduced to V(III) chromium is evaluated by difference of the volumes of titrant used in the first and third steps. Another example is the titration of a mixture of Fe(II) and V(IV) sulphates with Ce(IV) sulphate in dilute sulphuric acid in the first step Fe(II) is oxidised to Fe(III) and in the second jump V(IV) is oxidised to V(V) the latter change is accelerated by heating the solution after oxidation of the Fe(II) ion is complete. The titration of a substance having several oxidation states is exemplified by the stepwise reduction by acid chromium(II) chloride of Cu(II) ion to the Cu(I) state and then to the metal. 

The condensation is usually carried out by adding a solution containing equimolar amounts of the allyl halide and the aldehyde or ketone to a solution of at least two equivalents of chromium-(II) chloride in THF at 0 5°C. Frequently, the less precious component is used in 50-100% excess. Although commercially available anhydrous chromium(II) chloride can be utilized (Method B), its in situ preparation from chromium(III) chloride and lithium aluminum hydride (Method A) is often preferred. The removal of chromium and aluminum hydroxide, which are formed on aqueous workup, can be accomplished by filtration in the presence of a filtration aid. 

Chromium(II) Chloride Mediated Addition of Allyl Bromides to Aldehydes General Procedure12 ... 

Method B Alternatively, a suspension of 3.32 g (27 mmol) of anhyd chromium(II) chloride in THF is used. Chromium(If ) Mediated Addition ... 

A mixture of 10 mmol of the allyl bromide and 10-15 mmol of the aldehyde, dissolved in 20 mL of THF, is added dropwise at — 5 to 0°C to the chromium(II) chloride solution in THF prepared by method A or B. The mixture is stirred for 36 h at this temperature and then 15 mL of sat. sodium hydroxide and 20 g of anhyd Na2S04 are added stirring is continued for 20 min at 201C. The mixture is filtered over a pad of Celite/Na2S04 (7 l). The filtrate is concentrated and the residue purified, usually by chromatography on silica gel with pentane/diethyl ether or hexane/ethyl acetate. 

Ethyl (Z)-2-bromomethyl-2-heptenoate and aldehydes condense on reaction with chromium(II) chloride to furnish cw-3,4-disubstituted dihydro-3-methylene-2(3 //)-( uranones exclusively16, indicating that a (Z)-allylchromium complex might serve as reactive intermediate in the. mv-selec-tive addition step due to the bulky 2-substitucnt. Alternatively, an acyclic transition state for the reaction of the ( )-diastereomer, mediated by the Lewis acid dichloroaluminum hydride, has been discussed16. 

Benzyloxy-2-propenylchromium reagents are formed by the action of iodotrimethylsilane and chromium(II) chloride on 3,3-bis(benzyloxy)-l-propene in the presence of aldehydes, affording derivatives of anti-diols with good diastereoselectivity13. 

Oxygen-substituted allylchromium reagents are conveniently generated from vinyloxi-ranes by chromium(II) chloride in the presence of lithium iodide and aldehydes with high anti diastereoselectivity14. qh oh... 

A chiral nonracemic cyclic allyl iodide was shown to react with excess chromium(II) chloride and (4-methoxyphenylmethoxy)acetaldehyde to yield a single diastereomer, which was converted to la,25-dihydroxy vitamin D332. 

Double stereodifferentialing Hiyarna reactions are the key steps in the total synthesis of ( + )- and (-)-nephromopsinic acid12 and (-)- and ( + )-dihydrocanadensolide33. The enantiomcrically pure diterpene cycloaraneosene is assembled by two chromium(II) chloride mediated coupling reactions from (3S,87 )-9-benzyloxy-7-chloroirid-1-ene (3) and (3[Pg.444]

Drushel and Sommers96 also used zinc/hydrochloric add and Andreae97 chromium(II) chloride for reduction of sulphoxides. 

Redox titrants (mainly in acetic acid) are bromine, iodine monochloride, chlorine dioxide, iodine (for Karl Fischer reagent based on a methanolic solution of iodine and S02 with pyridine, and the alternatives, methyl-Cellosolve instead of methanol, or sodium acetate instead of pyridine (see pp. 204-205), and other oxidants, mostly compounds of metals of high valency such as potassium permanganate, chromic acid, lead(IV) or mercury(II) acetate or cerium(IV) salts reductants include sodium dithionate, pyrocatechol and oxalic acid, and compounds of metals at low valency such as iron(II) perchlorate, tin(II) chloride, vanadyl acetate, arsenic(IV) or titanium(III) chloride and chromium(II) chloride. 

Scheme 10 Chromium(II)chloride-promoted reductive couplings...

See Chromium(II) chloride See other metal oxonon-metallates, reducants... 

Chromium (II) chloride solutions can be prepared by any one of several different procedures. If pure electrolytic chromium is available, the procedure of Holah-Fackler (see synthesis 4) is recommended. Some modification as noted at the end of this procedure may be desirable. If metallic chromium is not available, commercial chromium(III) chloride may be reduced electrolytically (a suitable divided cell is needed), or the reduction may be effected by zinc and hydrochloric acid. The latter procedure, which starts with the most commonly available reagents and apparatus, is described here. 

After the chromium (II) chloride solution has been transferred to flask B, the flow of ammonia through the reaction vessel should be started. The ammonia delivery tube should approach but not dip below the liquid level in flask B. If tank ammonia is used, the tank should be opened carefully to avoid spattering of liquids by a sudden burst of gas. If ammonia is to be generated, the ammonium sulfate solution should be added carefully to the potassium hydroxide in flask C. It may be necessary to cool flask C with ice at first, then to warm the generator later in order to maintain a reasonably constant flow of ammonia. The use of tank ammonia avoids these problems. If zinc was used in the reduction, a precipitate of zinc hydroxide forms first and redissolves. The violet-blue solution stirred at 0° is saturated with ammonia, then a 2- to 3-g. sample of the platinum catalyst is added rapidly to flask B. A strong countercurrent of nitrogen is used to prevent entrance of air into the system when the catalyst is added. The reaction mixture is allowed to stir for one hour while the flask is cooled with ice. 

To the chromium (II) chloride solution prepared as described in the previous section, a 75-ml. aliquot of a 65% ethylene-diamine solution is added slowly with stirring. 

Comments on the Procedure if Other Methods for Preparation of Chromium(II) Chloride Are Used... 

If the chromium (II) chloride is prepared by the Holah-Fackler procedure from electrolytic chromium and hydrochloric acid, a three-necked round-bottomed flask may be used as a reaction vessel, and ammonia may be bubbled directly into the chromium(II) chloride solution using a T-joint in the nitrogen line. Bubbling of the ammonia through the liquid avoids the necessity for stirring. When the above procedure was used, it was necessary to centrifuge the final filtered solution at 2700 r.p.m. for 15 minutes in order to remove all the platinum catalyst. 

Chromium(II) chloride, 6 528t, 531, 564t Chromium(III) chloride, 6 532 physical properties, 6 528t Chromium(IV) chloride, 6 535 Chromium(III) chloride hexahydrate, physical properties, 6 528t Chromium chromate coatings, 76 219—220 Chromium complexes, 9 399 Chromium compounds, 6 526-571 analytical methods, 6 547-548 economic aspects, 6 543-546 environmental concerns, 6 550—551 health and safety factors, 6 548-550 hydrolysis, equilibrium, and complex formation constants, 6 530t manufacture, 6 538-543... 

Homoallylic amines result from the reaction of aldimines, previously activated by boron trifluoride etherate, with allylic bromides in the presence of chromium(II) chloride, e.g. equation 68194. 

Chromium(II) chloride, 4052 Cyclohexanone oxime, 2452 l,4-Dicyano-2-butene, 2311 Diethyl dicarbonate, 2444 Diethyl sulfate, Iron, Water, 1710 (Difluoroamino)difluoroacetonitrile, Hydrazine, 0630 Difluoroammonium hexafluoroarsenate, 0098 1,1-Difluorourea, 0398 Dihydroxymaleic acid, 1447 f Diketene, Acids, or Bases, or Sodium acetate, 1441 /V. /V-Dimcthylacctamidc. 1656... 

---