Anise aldehyde

Pyruvic Acid Compounds.—Lubrzynska and Smedley have recently shown that a number of aldehydes such as heliotropin, anisic aldehyde, benzaldehyde, and cinnamic aldehyde, condense with pyruvic acid in slightly alkaline solution, with the formation of )8-unsaturated-a-ketonic acids. For example, if heliotropin and pyruvic acid in alkaline solution be left standing for about eight days at ordinary temperature, dihydroxy-methylene-benzal-pyruvic acid is formed. This body forms yellow needles, melting at 163° Similarly, anisic aldehyde yields methoxy-benzal-pyruvic acid, melting at 130° and cinnamic aldehyde yields cinnamal-pyruvic acid, melting at 73°. 

Anisic aldehyde, CgHgOj, is a methyl ether of para-oxy-benzaldehyde, which is found to a small extent in the oils of fennel and aniseed. It is manufactured on an extensive scale artificially, and is the basis of all the perfumes of the hawthorn or May blossom type. It is known commercially as aubepine . A certain amount of anisic aldehyde is obtained as a by-product in the manufacture of coumarin, but the greater- part of it is obtained by very careful oxidation of anethol, the characteristic constituent of aniseed oil, which has the constitution—... 

This on methylation in the usual manner yields anisic aldehyde. Anisic aldehyde has the following constitution —... 

There is a solid aubepine met with in commerce, which appears usually to be the sodium bisulphite compound of anisic aldehyde. 

Anethol is the raw material from which most of the artificial hawthorn perfume is manufactured. This perfume consists of anisic aldehyde, known commercially under the name aubepine . 

Anisic aldehyde Pharma Aroma and Flavour Agrochemical C (Homo Het) 1000 - 3000 STR EC... 

Sometimes the unsaturated hydrocarbon is formed directly, as with benzyl chloride and anisic aldehyde /OCH3... 

Anisic Alcohol, 456 Anisic Aldehyde, 524 Anisole, 456, 606 Anisyl Acetate, 456, 568, 606 Anisyl Acetone, 524 Anisyl Alcohol, 456, 606 Anisyl Formate, 456, 607 Annatto Extracts, 31 Anthrone TS, (Sl)114 Antimony Trichloride TS, 850, 851 APDC Extraction Method, 766 APM, 35, (S 1)4 APM-Ace, (S3)5 APO, 32 Apocarotenal, 32 p-Apo-8 -Carotenal, 32 Apparatus for Tests and Assays, 4, 727 D-Araboascorbic Acid, 134 L-Arginine, 32, (S3)5 l-Arginine Monohydrochloride, 33 Arsenic Specification, Requirements for Keeping, xv... 

SYNS ANISIC ALDEHYDE FEMA No, 2670 4-METHOXYBENZALDEHYDE p-METHOXYBENZ-ALDEHYDE (FCC)... 

Some 4-substituted aromatic aldehydes, such as anisic aldehyde, toluic aldehyde, or t-butylbenzaldehyde, are produced commercially. The electrosynthesis can be accomplished by several different methods and is a good example of the versatility of selective electrochemical oxidations [91]. 

When a stream of ozonized oxygen or air, usually under 6% ozone, is passed through a solution of an olefin, such as 2,4,4-trimethyl-2-pentene, absorption occurs as fast as the ozone is introduced and no ozone escapes through the solution until all the olefin has been converted to ozonide. If an aromatic hydrocarbon such as benzene is ozonized rather than an aliphatic olefin, absorption of ozone is not complete and several times the theoretical amount of ozone must be used to effect complete ozoniza-tion. When a molecule has both an aromatic system and an aliphatic double bond, the aliphatic bond may react selectively, with little or no reaction with the aromatic system. Anethole will absorb a mole of ozone and produce, on hydrolysis of the ozonide, a very good yield of anise aldehyde. Complete saturation of the molecule requires almost 10 moles of ozone, however. 

In order to verify further these results the same investigations were carried out with anise seeds from Turkey and star anise from China which both contain trans-moihol as the main constituent. The formation of aldehyde during steam distillation was less pronounced compared to the fennel oils, although a 1.6-2.6 times higher content of anise aldehyde was detected in the steam distillates compared to the C02-extracts. The cA-anethol content was increased by 50% for the distillates, which confirms the results found for the fennel oils. 

Composition The ISO standard for aniseed [15] specifies the E-anethole content as 87-94%. Z-anethole (the more toxic isomer and transformation product of E-anethole when exposed to UV light [16]) is limited to 0.4%. The typical constituent of aniseed oil, pseudoisoeugenyl 2-methylbutyrate ]17] can occur up to 2%. Eor further confirmation of its natural origin by chirality GC, see ] 18]. Further constituents are methyl chavicol (up to 3%), gamma-himachalene (up to 5%), anisic aldehyde (up to 1.4%) and e.g. small amounts of monoterpenes. 

Composition According to ISO [19], the oil contains 86-95% E-anethole, up to 1.0% Z-anethole and up to 6.0% methyl chavicol. Eoeniculin can occur up to 3.0%, anisic aldehyde is limited to 0.5%. Further constituents are monoterpenes like a-pinene, a-phellandrene, limonene, linalool and a-terpineol. Besides P-caryophyllene, two further sesquiterpenes are typical trace components for Chinese star anise oil, namely E-and Z-a-bergamotene. 

Composition E-anethole (bitter fennel 55-75%, sweet fennel 80-95%), fenchone (bitter fennel 12-25%, sweet fennel below 1%), methyl chavicol (2-6%), limonene, a-pinene, a-phellandrene, cis-anethole and anisic aldehyde. For further constituents see [99,100]. Ravid et al. ]101] employed chirality GC to prove that enantiomerically pure (-i-)-fenchone is present in fennel oil. 

In the same way from anisic aldehyde and cuminol, there are obtained anisoln and cuminoi n, respectively ... 

Use Perfumes, particularly for dentifrices, flavors, synthesis of anisic aldehyde, licorice candies, color photography (sensitizer in color-bleaching process), microscopy. 

Next only to BHT, p-anisic aldehyde, also known as p-anisaldehyde, 4-methoxy benzaldehyde, or Aubepine is the second largest volume organic chemical made from p-cresol. Currently a few important world producers are manufacturing this product having multiple end uses. The major manufacturers are BASF (Germany), Nippon Shokubai (Japan), Atul (India). Koffolk Chemicals (Israel) and Laporte (USA) used to be the two important players but because of a number of reasons they have since then stopped production of p-anisic aldehyde. A few Indian companies apart from Atul have also started manufacture of this material. 

Uses of p-anisic aldehyde have been shown vide Fig. 5.2. 

From organic synthesis point of view, two steps are involved in the production of p-anisic aldehyde from p-cresol, namely, methylation of p-cresol to PCME and oxidation of PCME to p-anisic aldehyde... 

Table 5.2 Major Producers of Para-Anisic Aldehyde with Name Plate Capacities...

Production ofp-anisic aldehyde used for pharmaceuticals (Dilitiazem) requires much pure p-cresol (99%+). For sun screen agents (OMC) theoretically a lower quality (98-99%) p-cresol may be possibly used. Also, in metal plating, a lower quality p-anisic aldehyde (approx. 98% pure) is normally used. 

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