Vanillinum. Vanillin, CHO, U.S.P.

Vanilla planifolia, Andrews.  Methylprotocatechuic aldehyde occurring naturally in vanilla (cured fruit), or prepared synthetically.

Habitat.  E. Mexico, hot, damp woods, forests; cultivated in tropics.

Syn.  Vanilla Aromatica, Vaniglia; Fr. Vanille, Vanilline; Ger. Fructus (Siliqua)  Vanillae, Vanillin.

Va-nil'la.  L. fr. Sp. vainilla, formerly vaynilla, dim. of vaina (vayna), scabbard, sheath,  pod, lit. "little pod" -- i.e., pod resembling the sheath of a knife.

Pla-ni-fo'li-a.  L. planus, flat, + folium, leaf, flat-leaved -- i.e., leaves plain or flat,  without prominent veins.

Plant

Succulent, dark green, epiphytic, terrestrial or parasitic, perennial climber; stem long, 1-2 Cm. (2/5-4/5') thick, smooth, much branched, nodes with aerial roots and rootlets, 12.5-15 Cm. (5-6') long, for clinging to trees, frame-work, etc., leaves 10-15 Cm. (4-6') long, oval, tough, fleshy, veinless, dark green, paler beneath; flowers 5 Cm. (2') broad, pale yellowish-green, loose axillary racemes of 8-10.  Fruit (pod).  Vanilla, Vanilla Bean, N.F. -- The cured full-grown, unripe fruit, preserved in a cool place where it will not become brittle, when it should not be used.  It is linear, flattened, tapering, 12-35 Cm. (5-14') long, 5-9 Mm. (1/5-1/3') broad, in clusters of 3-15, flat circular scar at summit, curved (hooked) at base.  (Tahiti variety--middle broad, tapering similarly towards either end), blackish-brown, longitudinally wrinkled, moist-glossy, occasionally with efflorescence of vanillin acicular crystals, and 3-divided near tip; frequently cork patches; flexible, tough, 1-celled, blackish-brown pulp and many triangular, reticulate seed, .25-.30 Mm. (1/100-1/75') broad; odor and taste characteristic, very agreeable.  Test: 1. Efflorescent crystal on slide, + 1 drop of phloroglucinol T.S. and hydrochloric acid -- carmine-red (dist. from benzoic acid); solvent: 75 p.c. alcohol.  Dose, gr. 5-30 (.3-2 Gm.).

Commercial

Plant mostly cultivated, since 1850, from cuttings, sometimes seed, in Papantla, Misantla, Vera Cruz, Oaxaca provinces, where moisture is abundant and temperature never below 18 degrees C. (65 debrees F.); it climbs by rhizoids (non-absorbing roots), pollinates by insects, hand; bears fruit 3d year, continues 30-40; fruit (cured, full-grown, unripe) develops in 2-3 months, but a longer time is required for maturing, and when collected (late autumn before quite ripe, as green begins disappearing into yellow, to avoid splitting) is placed in heaps, sheltered from sun and rain, to undergo partial fermentation and shriveling, then followed by the process of "sweating" -- exposure to sun or stove heat (60 degrees C.)' 140 degrees F.) until a fine chestnut-brown color is acquired, and the odorous principle, vanillin, has been developed from the normal coniferin (secreted by the internal hair-like fibrillae), which is converted by hydrolization into glucose and coniferic alcohol, then this latter by an oxydase into vanillin -- the object being to drive moisture out upon the surface and finally drying the latter; the process may be aided by the sweating-box, steaming, wrapping in blankets, etc.; they now are dried by a 2-months' exposure to the sun, then coated with oil (that which exudes, also cocoa and cashew nut), tied in small bundles of 50-75, wrapped in foil, and marketed; by insufficient drying, to retain weight, the interior of beans and wherever tied sometimes become moldy.  There are several varieties: 1, Mexican (Vera Cruz) best, but beans vary much in value; 2, Bourbon, from Isle of Reunion, resembles Mexican, but beans blacker, tapering portion shorter, less firm and fleshy, surface smooth, waxy, soon becoming coated with acicular crystals (frost); odor more like Tonka bean; 3, Mauritius (Seychelles), often sold as inferior Bourbon; beans only 15 Cm. (6') long, 6 Mm. (1/4') broad, pale color, smooth, not waxy, faint odor; 4, South American (Guadeloupe), resembles Mexican, but broader, flatter, often 12 Mm. (1/2') broad, reddish-brown, odor of fermented molasses, pulpy, resinous, few crystals on surface, beans often open and seed on the surface; 5, Tahiti, transplanted Mexican; beans 15 Cm. (6')long, 12 Mm. (1/2') broad, reddish-brown, heliotrope odor; 6, Java, mostly consumed in Holland, beans 10-15 Cm. (4-6') long, fine flavor of Mexican but odor much more powerful; 7, Vanillons (Brazilian -- V. Pompo'na), larger, thicker than S. American, inferior vanilla odor (heliotrope), used by perfumers, tobacconists; contains vanillin .5 p.c.  Beans also are imported from Honduras, Madagascar, Martinique, etc., while some occur on the market deprived by a solvent of vanillin, and others to which benzoic acid, etc., have been added; all may be purchased as "splits" and "cuts."

Constituents

Fruit

Vanillin (Mexican 1.7 p.c., Bourbon 2 p.c., Java 2.75 p.c., in the 2 last associated with odorous oil), fixed oil 11 p.c., balsam, resin, sugar, mucilage, tannin, oxalic acid ash 4-6 p.c.

Vanilllinum. Vanillin. -- This is obtained (1) by crushing the pods (fruit) with sand, extracting with ether in a Soxhlet tube, shaking out ethereal extract with sodium sulphite solution, liberating vanillin from this by treating with sulphuric acid, expelling sulphurous acid generated, extracting with ether; (2) by slowly adding a concentrated solution of coniferin, CHO, from cambium sap of pines, to a warm solution of potassium dichromate in water and sulphuric acid, finally heating to boiling for 3 hours -- coniferin, by hydrolysis from action of acid, is converted into dextrose and coniferyl alcohol, and this latter oxidizes into vanillin and aldehyde: CHO + HO = CHO + CHO; CHO + O = CHO + CHO -- passing steam through mixture, or adding successive portions of ether, filtering, reclaiming ether, when vanillin crystallizes; (3) by boiling eugenol, CHO, with acetic anhydride, forming acetyl-isoeugenol, CH(CHO)O, which is oxidized with potassium dichromate into acetyl-vanillin -- the latter upon treating with potassium hydroxide solution and concentrating being converted into vanillin, which may be removed by acidulating filtrate with sulphuric acid and shaking out with ether; this method, owing to economic reasons, is used chiefly.  It is in fine, white, slightly yellowish, needle-like crystals, odor and taste of vanilla, 400 times stronger than the pod, soluble in alcohol, chloroform, ether, glycerin (20), water (100), hot water (16), aqueous solutions of alkali hydroxides, from which it is precipitated by acids; melts at 81 degrees C. (178 degrees F.); incinerate -- ash .05 p.c.; aqueous solution acid, optically inactive.  Tests: 1. Aqueous solution with ferric chloride T.S. -- blue color, changed to brown on boiling, and on cooling -- white precipitate (dihydrodivanillin).  2. Shake ethereal solution with saturated aqueous solution of sodium bisulphite, add sulphuric acid -- vanillin precipitated.   3. Cold aqueous solution with lead acetate T.S. -- white precipitate (lead compound of vanillin), soluble in hot water.  4. Warm .1 Gm. with concentrated alcoholic solution of sodium hydroxide, + a drop of chloroform, warm -- no odor of phenylisocyanide (abs. of acetanilid).  Impurities: Acetanilid, benzoic acid, boric acid, terpin hydrate, coumarin, 50-90 p.c.  Should be kept dark, in well-closed containers.  Dose, gr. 1/6-1/2 (.01-.03 Gm.).

Preparations

1.  FRUIT: 1. Tinctura Vanillae, N.F., 10 p.c. + sucrose 20 (1st menstruum alcohol, 2d diluted alcohol): Preps.: 1. Elixir Ammonii Valeratis, N.F., 1.6 p.c. 2. Emulsum Olei Ricini, N.F., 2.5 p.c. 3. Syrupus Bromidorum, N.F., 3.2 p.c. 4. Syrupus Cacao, N.F., 1/5 p.c. 5. Tabellae Santonini, N.F., 1/4 m.  6. Tabellae Santonini Compositae, N.F., 1/4 m.  II.  VANILLIN: 1. Spiritus Vanillini Compositus, N.F., 20 p.c.: Prep.: 1. Elixir Vanillini Compositum, N.F.,  20 p.c.  2. Elixir Amygdalae Compositum, N.F., 1/10 p.c.  3. Liquor Ferri Peptonati, N.F., 1/500 p.c.  4. Liquor Ferri Peptonati et Mangani, N.F., 1/500 p.c.  5. Oleum Ricini Aromaticum, N.F., 1/10 p.c.

Properties

Carminative, stimulant, aphrodisiac, antihysteric, irritant.  Those working in it have itching hands, face, neck (the skin being covered with pruriginous eruptions), dizziness, weariness, muscular pains; eruptions due to an acarus which does not enter the skin.

Uses

The Spanish conquerors found vanilla in use in Mexico for flavoring chocolate, etc., and while now recommended for hysteria, it is employed chiefly as a flavoring agent, being the most general of all substances; large quantities may produce poisonous symptoms.  Vanilla Pompo'na, Guadeloupe variety, V. Gardne'ri, Brazilian and Bahia, V. odora'ta, V. phaen'tha, Jamaica, Trinidad -- used similarly.