4- -valeronitrile

To a solution of 100 g. (0.91 mole) of catechol in 200 ml. of methanol is added 75 g. (0.60 mole) of methyl sulfate (Caution—toxic substance), and the resulting mixture is cooled to —5°. A solution of 150 g. (3.8 moles) of sodium hydroxide in 350 ml, of water is added all at once. Several minutes after the vigorous reaction has subsided, excess water is added and the oily layer is removed by ether extraction. The ethereal solution is washed several times with water, dried, and distilled to give a 95% yield of veratrole, b.p. 205° at atmospheric pressure, m.p. 15°. 

---

For practice, the student should carry out both alkaUne (compare Section 111,83) and acid hydrolysis of acetonitrile, n-valeronitrile (n-butyl cyanide) and n-capronitrile (n-amyl cyanide). 

Catalysts show remarkable product variation in hydrogenation of simple nitriles. Propionitrile, in neutral, nonreactive media, gives on hydrogenation over rhodium-on-carbon high yields of dipropylamine, whereas high yields of tripropylamine arise from palladium or platinum-catalyzed reductions (71). Parallel results were later found for butyronitrile (2S) and valeronitrile (74) but not for long-chain nitriles. Good yields of primary aliphatic amines can be obtained by use of cobalt, nickel, nickel boride, rhodium, or ruthenium in the presence of ammonia (4J 1,67,68,69). 

Diphenylacetonitrile is condensed with 2dimethyl-amino)-2,2-diphenyl valeronitrile. It is then reacted with ethyl magnesium bromide and then hydrolyzed using HCl to give methadone hydrochloride. 

Diphenyl diazomethane Benztropine mesylate a/l -Diphenyl-7.dimethylamino valeronitrile Aminopentamide Diphenylmethane... 

Controlled potential electrolysis of the substrates, at —1.4V vs. SCE, at a carbon felt electrode on which only 3.6x10" mol Bjj were immobilized (approx. 1 X 10 ° mol cm" ) resulted in the production of 76pmol of valeronitrile 16, corresponding to a turnover number of 2100 This example shows that the combination of inner sphere redox mediators and high surface electrodes is promising. 

The Hydrogenation of Pyridine-3-Carbonitrile and Valeronitrile. Table 57.4 displays the effect of FT on the 1° amine yields and reaction rates of pyridine-3-carbonitrile (P3C) and valeronitrile (VN). Unlike with the hydrogenation of BN,... 

Vitamin B12 derivatives are also effective catalysts for the electroreductive cyclization of bromoalkenes in conductive microemulsions,299 300 or for ring-expansion reactions in cyclic a-(bromomethyl)-(3-keto esters in DMF.301 Vitamin Bi2 attached to an epoxy-polymer has been used in electrosynthesis of valeronitrile by reductive coupling of iodoethane and acrylonitrile.302... 

Reaction yields and regioselectivity were comparable, or better, than those obtained with more simple nitrile oxides. Examples of the use of an optically active (R)-4-chloro-valeronitrile JV-oxide for the synthesis of non-racemic isoxa-lines 371d and 371e are also reported [93]. 

Valeraldehyde, p28 Valeric acid, p38 Valeronitrile, p35 Valeryl chloride, p45 Vanillic acid, hi43 Vanillin, hl42 Vanillyl alcohol, hl45 Veratraldehyde, d492 Veratric acid, d496 Veratrole, d493 Veronal, d330... 

VINYL PROPIONATE 2-HYDROXYETHYL ACRYLATE LEVULINIC ACID METHYL ACETOACETATE GLUTARIC ACID VALERONITRILE n-BUTYL ISOCYANATE N-HETHYL-2-PYRROLIDONE L-GLUTAMIC ACID CYCLOPENTANE 2-METHYL-1-BUTENE... 

The most popular thermal initiator is 2, 2 -azobisisobutyronitrile (AIBN), with a half-life (ti/2) of 1 h at 81 °C and 10 h at 65 °C in toluene [8,21]. Generally, 5-10 mol% of initiator is added either all in one portion or by slow addition over a period of time. There are other azo compounds which can be chosen, depending on the reaction conditions. Indeed, the nature of the substituent play an important role as can be seen for 2, 2 -azobis-(4-methoxy)-3,4-dimethyl-valeronitrile (AMVN), with a ti/2 of 1 h at 56 °C and 10 h at 33 °C in toluene. There are also hydrophilic azo compounds, such as 2, 2 -azobis-(2-methylpropionamidine) dihydrochloride (APPH), with a ti/2 of 10 h at 56 °C in water. 

Diorganyl tellurides add to alkynes via a radical mechanism in the presence of a catalytic amount of a radical initiator such as AIBN or 2,2 -azobis(4-methoxy-2,4-dimethyl-valeronitrile) (In), as well as under irradiation by visible light (tungsten lamp), affording vinylic tellurides in a variable ZIE ratio." ... 

The synthesis of eprosartan mesylate (6) by SmithKline Beecham Pharmaceuticals is described in Scheme 9.9. The synthesis of the precursors 43 and 45 were required for imidazole formation. Thus, valeronitrile (40) was converted to the imidate salt 41 with... 

---