Nonane production

TABLE 6.3. Process for optimized nonanal production of 100 000 tonnes y1 using perfluoro-methylcyclohexane in a fluorous biphasic system a... 

TABLE 7.6. Process characteristics for optimised nonanal production (using liquid-liquid biphasic catalysis with ionic liquids) and butanal production (using SILP catalysis) on a 100.000 tons/year scale... 

The use of chiral dirhodium tetraprolinate catalysts, such as 87 and 88, allows asymmetric induction resulting in formation of azabicyclo[3.2.2]nonane products with high enantiomeric excess <2002JOC5683>. 

In terms of hydroisomerization selectivity, it was found that Pt/ZSM-22 exhibits highest selectivity for the conversion of n-alkanes to 2-methyl-branched isomers 308,309). For example, the dibranched isomers from n-decane are particularly rich in 2,7-dimethyloctane. On the other hand, 3-, 4-, and 5-methylnonane isomers are significant even at a low conversion level on Pt/H-USY zeolite. On Pt/H-USY, the composition of the methyl-nonane product fraction approaches thermodynamic equilibrium at medium levels of conversion through methyl shifts. In addition, ethyloctanes are observed as primary products on Pt/H-USY via substituted protonated cyclobutane, but they are absent from the reaction products with Pt/ZSM-5... 

Illustrative of a two-atom expansion process, a bicyclo[3.2.2]-nonane product was derived from a 1,3-shift of a norbomene derivative... 

The thioboration of terminal alkynes with 9-(alkylthio)-9-borabicyclo[3.3.1]-nonanes (9-RS-9-BBN) proceeds regio- and stereoselectively by catalysis of Pd(Ph,P)4 to produce the 9-[(Z)-2-(alkylthio)-l-alkeny)]-9-BBN derivative 667 in high yields. The protonation of the product 667 with MeOH affords the Markownikov adduct 668 of thiol to 1-alkyne. One-pot synthesis of alkenyl sulfide derivatives 669 via the Pd-catalyzed thioboration-cross-coupling sequence is also possible. Another preparative method for alkenyl sulfides is the Pd-catalyzed cross-coupling of 9-alkyl-9-BBN with l-bromo-l-phe-nylthioethene or 2-bromo-l-phenylthio-l-alkene[534]. 

D. ci - -Thiabicyclo[4 .. Q]nonan S,S-Dioxide [Benzo[c]thiophene 2,2-dioxide, cis-octahydro-]. A solution of the sulfide (43.0 g., 0.303 mole) in 11. of ether is cooled to 0° and treated dropwise while magnetically stirred with 1.01. of 0.65iV ethereal monoperphthalic acid (0.65 mole). The mixture is kept overnight at 0°, after which time the precipitated phthalic acid is separated by filtration and the filtrate concentrated with a rotary evaporator. Bulb-to-bulb distillation of the residual oil at 0.05-0.1 mm. affords the sulfone as a eolorless liquid (48.5-50 g., 92-95%) (Note 11). This product is crystallized from ether-hexane to give a colorless solid, m.p. 39-41° (Note 12). 

An interesting variant of this reaction is the formation of 2-thiaadamantane-4,8-dione by hydrolysis of the reaction product of the bispyrrolidine enamine of bicyclo[3.3.1]nonane-2,6-dione with sulfur dichloride (106). 

Spirapril (37) is a clinically active antihypertensive agent closely related structurally and mechanistically to enalapril. Various syntheses are reported with the synthesis of the substituted proline portion being the key to the methods. This is prepared fkim l-carbobenzyloxy-4-oxopro-line methyl ester (33) by reaction with ethanedithiol and catalytic tosic acid. The product (34) is deprotected with 20% HBr to methyl l,4-dithia-7-azospiro[4.4 nonane-8-carboxylate (35), Condensation of this with N-carbobenzyloxy-L-alanyl-N-hydroxysuccinate leads to the dipeptide ester which is deblocked to 36 by hydrolysis with NaOH and then treatment with 20% HBr. The conclusion of the synthesis of spirapril (37) follows with the standard reductive alkylation [11]. 

To a solution of 11.8 g of 2-A-pyrrolidylbicyclo[3.3.1]nonan-9-one in 25 ml of dry ether is added 25 g of methyl iodide in one portion. The solution is allowed to stand at room temperature for 2 hours, then filtered to remove the product. To the filtrate is added 5 g of methyl iodide and after 5 hours at room temperature, solid is again collected. A third crop is similarly obtained. The combined solids (approx. 17 g) are recrystallized from acetone-ethanol to give about 16 g of the methiodide, mp 220-222°. 

Bicyclof 3.3.1 ]nonane-2,6-dione (10) A solution of 10 g of Meerwein s ester, 30 ml of glacial acetic acid, and 20 ml of 6 A hydrochloric acid is heated under reflux for 10 hours. The solution is then carefully distilled under aspirator pressure until all volatile materials (water and acetic acid) are removed. The solid residue is distilled at 129-131°/4 mm to afford the product. It may be recrystallized from benzene giving about 3 g of bicyclo-[3.3.1]nonane-2,6-dione, mp 138-140°. 

When the valence tautomeric mixture of oxepin and benzene oxide is treated with singlet oxygen, the primary product is the 1,4-endoperoxide 3 which has proven to be too labile for isolation.219 Its formation can be rationalized by a 1,4-addition across the diene system of the benzene oxide structure 3 then rearranges to ba s-3,6,9-trioxatetracyclo[6.1.0.02 4.05 ]nonane (transbenzene trioxide, 4). 

A related reaction is the addition of l,l,2-trichloro-2-nitrosoethene to the oxepin/benzene oxide mixture. The primary adduct cannot be isolated but the rearrangement product 9-(tri-chlorovinyl)-tra . -3,6-dioxa-9-azatetracyclo[6.1.0.0z,4.05,7]nonane (6) is obtained in 17% yield.221... 

To a solution of 3.5 uiL (25 mmol) of trimethylsilylacetylcne in 40 mL of THF are added dropwise, at — 78 °C, 10.4 mL of 2.5 M BuLi (26 mmol) in hexane. After stirring for 15 min at —78 X, 25 mL of 1 M 9-methoxy-9-borabicyclo[3.3, l]nonane in hexane are added. The mixture is stirred at —78 "C for a further 1.5 h. Then, 4 mL (33 mmol) of BF3 OEt2 are added and the mixture is stirred for an additional 15 min at — 78 °C before being allowed to warm to r.t. The volatiles are evaporated under reduced pressure to afford a white solid. After the addition of 25 mL of pentane, the suspension is stirred for a few minutes and allowed to settle. The supernatant liquid is decanted into a second flask via a double-ended needle. This procedure is repeated twice, each time with 10 mL of pentane. The combined pentane solution is cooled to — 78 X to precipitate the product. The mother liquor is removed and the crystals are dried under vacuum to afford an extremely hygroscopic, white crystalline material yield 6.52 g (90%). 

The silicon- and sulfur-substituted 9-allyl-9-borabicyclo[3.3.1]nonane 2 is similarly prepared via the hydroboration of l-phenylthio-l-trimethylsilyl-l,2-propadiene with 9-borabicy-clo[3.3.1]nonane36. The stereochemistry indicated for the allylborane is most likely the result of thermodynamic control, since this reagent should be unstable with respect to reversible 1,3-borotropic shifts. Products of the reactions of 2 and aldehydes are easily converted inlo 2-phenylthio-l,3-butadienes via acid- or base-catalyzed Peterson eliminations. 

Enantioselective reduction is not possible for aldehydes, since the products are primary alcohols in which the reduced carbon is not chiral, but deuterated aldehydes RCDO give a chiral product, and these have been reduced enantioselectively with B-(3-pinanyl)-9-borabicyclo[3.3.1]nonane (Alpine-Borane) with almost complete optical purity. ... 

Reaction products were analyzed by on-line gas chromatography with a Shimadzu GC-14A gas chromatograph equipped with a 50 m CP Sil-5 fused silica capfllary column and a flame ionization detector. Reaction intermediates were identified by GC-MS. Samples were taken after 50 h on stream when the activity of the catalyst was stable, with n-nonane and n-dodecane as internal standards. Space time was defined as t = e Voat/vgas, where e is the void fraction of the... 

The possibility of carrying out a multistep synthesis makes it possible to obtain P,B-containing derivatives from unstable intermediate a-hydroxyalkylphosphines. Thus, phenylphosphine, salicylic aldehyde, phenylboric acid anhydride, and triethylamine interact to give a bicyc-lic product—2,8,9-trioxa-1 -borata-4-phospha-6,7 -benzobicyclo [3,3,3] nonane (115) [Eq. (74)] (87IZV2118 89IZV946). In this case an aldehyde takes part in the reaction opening up new synthetic possibilities. 

Transannular interactions lead to ring closures and reductions to adamantane compounds when dienes of the bicyclo[3.3.1]nonane family are treated with Brpnsted acids and triethylsilane. Compounds 48-51 form reaction mixtures containing various amounts of products 52-54 (R = OH, O2CCF3, Cl) under such conditions.243 The best yields of hydrocarbon 52 occur when the dienes are treated with a 25% excess of sulfuric acid and a 50% excess of triethylsilane in dichloromethane at 20°.243 The stereospecific nature of these transannular reductions is demonstrated by the observation that the enantiomeric purity of the chiral diene 55 is retained in the chiral hydrocarbon product 56 (Eq. 98).243 Dienes of... 

Induced Phase Separation is also a good choice for octene hydroformylation. Octene can easily dissolve in the organic based catalyst solution, and with addition of small amounts of water, nonanal and its condensation products will readily separate from the sodium salt of a monosulfonated phosphine. To choose between Liquid Recycle and Induced Phase Separation would require a detailed technical and economic study that is outside the scope of this chapter. 

The use of a water-soluble phosphine based catalyst is not a preferred choice for octene hydroformylation. Although separation of nonanal and its condensation products from an aqueous catalyst should be facile, forming nonanal at a commercially viable rate could be challenging. In order to react, octene needs to be in the same phase as the catalyst, and octane has very low solubility in water. 

Finally, water extraction of nonanal and its condensation products is totally impractical. 

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