Aluminums methylene

When heated for eight hours at 200°C and 91.2 MPa (900 atm) in the presence of aluminum, methylene chloride reacts with carbon monoxide to yield chloroacetyl chloride, CH2CICOCI (10). 

The present cyclopropanation using trialkyl aluminum-methylene iodide may proceed via dialky1(1odomethyl)a1uminum as an active intermediate, which can be also generated by the reaction of di alky aluminum iodide with diazomethane. In addition, reaction of diiodomethane with triisobutyl-... 

Contact with iron or strong oxidizers may cause fires and explosions may react violently with alkyl aluminums. Methylene diisocyanate can polymerize violently on contact with DMF. 

A reactive titanium carbene intermediate is formed from a stable bridged titanium—aluminum methylene complex. 

Reduction of amides (Section 22 9) Lithi um aluminum hydride reduces the car bonyl group of an amide to a methylene group Primary secondary or tertiary amines may be prepared by proper choice of the starting amide R and R may be ei ther alkyl or aryl... 

Diketene is used to C-acetoacetylate aromatic compounds in the presence of aluminum trichloride [7446-70-0]. Benzene [71-43-2] and diketene react to produce acetoacet5lben2ene [93-91-4]. Pyrrole [109-97-7] and diketene react to produce 2-acetoacet5lpyrrole [22441-25-4]. The C-acetoacetyl derivatives of active methylene compounds such as cyanoacetates, malonodinitrile [109-77-3] and Meldmm s acid [2033-24-1], and olefins can be prepared using diketene. 

Aluminum chloride dissolves readily in chlorinated solvents such as chloroform, methylene chloride, and carbon tetrachloride. In polar aprotic solvents, such as acetonitrile, ethyl ether, anisole, nitromethane, and nitrobenzene, it dissolves forming a complex with the solvent. The catalytic activity of aluminum chloride is moderated by these complexes. Anhydrous aluminum chloride reacts vigorously with most protic solvents, such as water and alcohols. The ability to catalyze alkylation reactions is lost by complexing aluminum chloride with these protic solvents. However, small amounts of these "procatalysts" can promote the formation of catalyticaHy active aluminum chloride complexes. 

Other, removable cation-stabilizing auxiliaries have been investigated for polyene cyclizations. For example, a sdyl-assisted carbocation cyclization has been used in an efficient total synthesis of lanosterol. The key step, treatment of (257) with methyl aluminum chloride in methylene chloride at —78° C, followed by acylation and chromatographic separation, affords (258) in 55% yield (two steps). When this cyclization was attempted on similar compounds that did not contain the C7P-silicon substituent, no tetracycHc products were observed. Steroid (258) is converted to lanosterol (77) in three additional chemical steps (225). 

Methylene chloride is one of the more stable of the chlorinated hydrocarbon solvents. Its initial thermal degradation temperature is 120°C in dry air (1). This temperature decreases as the moisture content increases. The reaction produces mainly HCl with trace amounts of phosgene. Decomposition under these conditions can be inhibited by the addition of small quantities (0.0001—1.0%) of phenoHc compounds, eg, phenol, hydroquinone, -cresol, resorcinol, thymol, and 1-naphthol (2). Stabilization may also be effected by the addition of small amounts of amines (3) or a mixture of nitromethane and 1,4-dioxane. The latter diminishes attack on aluminum and inhibits kon-catalyzed reactions of methylene chloride (4). The addition of small amounts of epoxides can also inhibit aluminum reactions catalyzed by iron (5). On prolonged contact with water, methylene chloride hydrolyzes very slowly, forming HCl as the primary product. On prolonged heating with water in a sealed vessel at 140—170°C, methylene chloride yields formaldehyde and hydrochloric acid as shown by the following equation (6). 

Dry methylene chloride does not react with the common metals under normal conditions however, a reaction with aluminum can be initiated, sometimes explosively, by the addition of small amounts of other halogenated solvents or an aromatic solvent (7). Iron catalyzes the reaction, and this can be significant in the handling and storage of methylene chloride and in the formulation of products, eg, in aluminum aerosol containers of pigmented paints, where the conditions necessary for the reaction are commonly found. A typical reaction in this process is shown in equation 2. 

Further dechlorination may occur with the formation of substituted diphenyhnethanes. If enough aluminum metal is present, the Friedel-Crafts reactions involved may generate considerable heat and smoke and substantial amounts of hydrogen chloride, which reacts with more aluminum metal, rapidly forming AlCl. The addition of an epoxide inhibits the initiation of this reaction by consuming HCl. Alkali, alkaline-earth, magnesium, and zinc metals also present a potential reactivity hazard with chlorinated solvents such as methylene chloride. 

Bromochloromethane is produced by reaction of an excess of a mixture of methylene chloride and bromine with aluminum at 26 to 30°C (9). 

Diphenylmethane has been prepared with aluminum chloride as a catalyst from methylene chloride and benzene, from chloroform and benzene as a by-product in the preparation of triphenylmethane, and from benzyl chloride and benzene. It has been prepared by the reduction of benzophenone with hydriodic acid and phosphorus, or with sodium and alcohol. It has also been made by heating a solution of benzyl chloride in benzene with zinc dust, or with zinc chloride. The above method is only a slight modification of the original method of Hirst and Cohen. ... 

Some advantages of this reaction are high yield if the tosylate is in a sterically accessible position excellent isotopic purity of the product (usually higher than-95%) and perhaps most important, access to stereospecifically labeled methylene derivatives. For example, deuteride displacement of 3j -tosylates (183) yields the corresponding Sa-d derivative (185) in 96-98% isotopic purity. Application of this method to the labeled sulfonate (184), obtained. by lithium aluminum deuteride reduction of a 3-ketone precursor (see section HI-A) followed by tosylation, provides an excellent synthesis of 3,3-d2 labeled steroids (186) without isotopic scrambling at the adjacent positions. The only other method which provides products of comparable isotopic purity at this position is the reduction of the tosyl-hydrazone derivative of 3-keto steroids (section IV-B). 

The course of the ring opening in epoxides derived from various exocyclic methylene compounds by treatment with lithium aluminum deuteride has been studied in the norbornane series. ... 

The introduction of the l/, 2j5-methylene function into cortical hormones is best carried out by starting with the A -3)S-aIcohols (7) which are prepared by lithium aluminum hydride or lithium tri-t-butoxyaluminum hydride reduction of the corresponding A -3-ketones. 

Triflates of aluminum, gallium and boron, which are readily available by the reaction of the corresponding chlorides with triflic acid, are effective Fnedel-Crafis catalysis for alkylation and acylation of aromatic compounds [119, 120] Thus alkylation of toluene with various alkyl halides m the presence of these catalysts proceeds rapidly at room temperature 111 methylene chloride or ni-tromethane Favorable properties of the triflates in comparison with the correspond mg fluorides or chlorides are considerably decreased volatility and higher catalytic activity [120]... 

The salts of 3-acetyl-18/3-glycyrrhetinic acid can be prepared by reaction between 3-acetyl-18/3-glycyrrhetinic acid and an aluminum alcohoiate. Preferably lower alcoholates are used, i.e., alcoholates in which the alkoxy group or groups have from one to four carbon atoms. The salification reaction may be carried out at room temperature or at an elevated temperature in conventional fashion, preferably in the presence of organic solvents. As organic solvents may be used alcohols, ethers, ketones, chlorinated solvents (methylene chloride, chloroform) ethyl acetate, etc. 

A solution of 3.5 g 4-(2,3-epoxypropoxy)carbazole in 50 ml absolute alcohol is mixed with 30 ml isopropylamine and heated for 3 hours under reflux. When the reaction is finished, the reaction mixture is evaporated to dryness. The residue obtained is taken up in methylene chloride and chromatographed over an aluminum oxide column (300 g basic aluminum oxide, activity stage IV eluent methylene chloride). The eluted fractions are evaporated and the residue is dissolved in methanol and acidified with 2N ethereal hydrochloric acid. 

The process can also be carried out without solvent )methylene chloride by adding a slight excess of aluminum chloride powder to a solution of one mol of dichloroanisole and one mol of acid chloride. 

To optimize the alkylation conditions, ferrocene was reacted with allyldimethyl-chlorosilane (2) in the presence of various Lewis acids such as aluminum halides and Group lO metal chlorides. Saturated hydrocarbons and polychloromethanes such as hexane and methylene chloride or chloroform were used as solvents because of the stability of the compounds in the Lewis acid catalyzed Friedel-Crafts reactions. The results obtained from various reaction conditions are summarized in Table IV. 

As shown in Table IV, the highest catalytic activity of metal halides used as Lewis acid for the alkylation reaction of ferrocene with 2 was observed in methylene chloride solvent. Among Lewis acids such as aluminum chloride, aluminum bromide, and Group 4 transition metal chlorides (TiCl4, ZrCU, HfCU), catalytic efficiency for the alkylation decrea.ses in the following order hafnium chloride > zirconium chloride > aluminum chloride > aluminum bromide. Titanium chloride... 

---