CA1336127C - Process for preparing natural benzaldehyde and acetaldehyde, natural benzaldehyde and acetaldehyde compositions, products produced thereby and organoleptic utilities therefor - Google Patents

Abstract

Described is a process for preparing natural benzaldehyde and acetaldehyde and compositions of matter containing natural benzaldehyde and acetaldehyde as well as products produced thereby and organoleptic utilities therefor, which process comprises the step of contacting with base naturally occurring cinnamaldehyde or a natural product rich in cinnamaldehyde such as Ceylon oil of cinnamon, Ceylon cinnamon bark, Saigon cinnamon bark, cassia oil, Ceylon cinnamon quills, cinnamon leaf oil, oil of cinnamon Madagascar or the like according to the reaction:

the reaction taking place in the absence of any other reagents except inert solvent.

Described and claimed is an apparatus for carrying out said process.

Description

B~CKGROUND OF THE INVENTION

A major use of natural benzaldehyde is as an ingredient in "natural" cherry flavor and other flavors for augmenting or enhancing the aroma or taste of consumable materials including foodstuff~, chewing gums, medicinal products, toothpastes, chewing tobacco, smoking tob~cco and smoking tobacco articles.

A ma~or use of natural acetaldehyde is as an ingredient ln "natural" orange flavor and other flavors for augmenting or enhancing the aroma or taste of consumable materials including foodstuffs, chewing gums, medicinal products, toothpastes and chewlng tobacco.

Natural benzaldehyde has been used in natural cherry flavors in the form of an apricot kernel derivative as is taught in U.S. Letters Patent 1,416,128 issued on May 16, 1922. An undesirable feature of the known processes for preparing natural benzaldehyde from apricot kernels or reground press cake i8 that along with the benzaldehyde, toxic hydrocyanic acid is produced which must be separated completely from the benzaldehyde and from the re~t of the oil prior to use. Other techniques for producing natural benzaldehyde are known but these techniques produce it in such yields as to cause the resulting process to be uneconomical. For example, Hockenhull, et al, Biochem. J., 50, 605-9, (1952) (Title: "Oxidation of Phenylacetic Acid by Penicillium chrysogenum")discloses i production of benzaldehyde starting with phenylacetic acid through either benzyl alcohol or mandelic acid via the sequences:

P~.~H,.COO~
P~ LO cit +O +O
-~o ~.C9~0~ P~.C~OH.COO~
b~cohol m-ntelic ~id ~ ~ - CO, , ., --CO, .P~.CHO~ Ph.CO.COO~
'IJhr~ ~id, ~ I

! 4 Towers, et al, Can. J. Zool. 1972, 50(7), 1047-50 . ("Defensive secretion:biosynthesis of hydrogen cyanide and benzaldehyde'from phenylalanine by a millipedeU) discloses a biosynthetic pathway for the production of benzaldehyde from dietary phenylalanine in Oxidus gracilis, thusly:

O
~0 C=-~--O

HCI~/ + ~lJ~ <.

Halpin, et al, Biochemistry, 1981, Volume 20, pages ~1525-1533 (Title: "Carbon-13 Nuclear Magnetic Resonance Studies of Mandelate Metabolism in Whole Bacterial Cells and in Isolated, in Vivo Cross-Linked Enzyme Complexes") discloses the :~ biochemical pathway from mandelate ion to benzaldehyde, thusly:

~ 'eJAte ~ (L)~ te X~ ~ ~ d~yL~se ~13~ At~
~8~ ~

~,7~l~de/

~,li_o ~

i~

Reeves, et al, TAPPI 48(2), pages 121-5, (1965) (Title:
"Reaction Products Formed Upon the Alkaline Peroxide Oxidation of Lignin-Re~ated Model Compounds") discloses the effect of ;.alkaline hydrogen pero~ide oxidation on cinnamaldehyde whereby the cinnamaldehyde is split at the double bond with the formation of the corresponding benzaldehyde and benzoic acid ', according to the reaction:
,,., O

t ~ 11202 ~ ~7 At page 124, column 1, paragraph 1, Reeves~ et al theorizes that a "reverse aldol reaction" is not responsible for the formation of vertraldehyde due to the fact that acetaldehyde the other product of the potential "reverse aldol reacton"
was not obtained. Therefore, our discovery of the "retro-aldol"
reaction taking place, to wit:

~ ~ ~sE]

was unexpected and unobvious. The "retro-aldol" reaction, to wit:

.

~~~ [Bl3sE~ ~ Jl~

indeed, took place due to the different reaction conditions from those proposed and set forth in Reeves, et al; different insofar as temperature of reaction and time of reaction are concerned; longer times of reaction and higher temperatures of reaction being the conditions in our "retro-aldol" reaction as opposed to shorter times of reaction and lower temperatures insofar as the Reeves, et al reaction is concerned.

In our own invention, no reagents other than base and naturally occurring cinnamaldehyde and solvent are utilized to carry out the "retro-aldol" reaction of our invention, to wit:

~o rB~S~]> ~

The process of our invention thus gives rise to unobvious, unexpected and advantageous results and represents an advance in the art i~ the production of "natural n benzaldehyde taken alone or in combination with natural cinnamaldehyde; and, further, in the production of ~natural acetaldehvde.-~ -8- 1 3361 27 SU~-D~ARY OF ~HE INVENTION

Our invèntion is directed to the production of "natural"
benzaldehyde and/or "natural n acetaldehyde taken alone or in admixture with "natural" c~nn~ ~ldehyde according to a reaction where "natural" cinnamaldehyde is subject to a "retro-aldol"
reaction, thusly:

t8~5E] ~ 1 The cinnamaldehyde reactant may occur in either the "cis" form having the structure:

~0 , and/or the "trans" form having the structure:

O .. , ~, .. . .

g The cinnamaldehyde may be in recovered form from natural sour-ces as by distillation or extraction or the cinnamaldehyde may exist in its natural state immediately prior to the reaction, thusly:
(i) Oil of Cinnamon Ceylon;
(ii) Ceylon cinnamon Bark (Cinnamomum zeylanicum Nees ex Blume (fam.La~raceae)):
(iii) The Rark of Saigon cinnA ~n (Cinnamomum loureirii Nees (fam.Lauraceae):
(iv) The Bark of Cassia cinnamon (ex Cinnamomum cassia (Nees)) Nees ex Blume (fam. Lauraceae):
(v) The Bark of Saigon cin~A -n :
(vi) Oil of cinnamon Bark Ceylon;
(vii) "Quills" from Ceylon cinnamon ( including "fines","Barcelona" and "Hamburg"):
(viii) Ceylon cinnamon quillings and featherings:
(ix) Ceylon cinn~ -n chips:
(x) Ceylon Cinna ~ n bark oil:
(xi) Oil of cinnamon Seychelles:
(xii) Oil of cinnamon Madagascar:
(xiii) Leaves of Cassia;
(xiv) Cassia Bark (Cassia lignea)in ground or powdered form;
(xv) Oil of CaQsia.

Thus, the cinn al~ehyde source may be treated with a base such a~ sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, lithium bicarbonate, magnesium hydroxide, calcium hydroxide, calcium carbonate, proline having the structure:

O
~OH

i 1 3361 27 choline having the structure:

[0~]~

, f~O

or a natural choline source such as natural lecithin having the ~structuro:

rH2 - O R

;H - O - ~ - R' CHz - O - - O - CH2 - CH2 - N - CH3 ~ a CH3 in the presence of base (wherein the residues:

//o C//
R \~, represent palmitoyl, stearoyl, oleyl, linoleyl, linolenyl and C20-C22 acid residues) rexamples of naturally occurring lecithin are soybean lecithin (reference: "Soybeans, Volume II, (Inter-science Publishing Company, New York, 1951), pages 593-647 and natural phosphatide lecithi~ whereby a "retro-aldol" reaction takes place, thusly: , ~ ~B-9sE] ~

A requirement of our invention is that no other reagents be present which would cause the reaction to give rise to a composition containing benzaldehyde or acetaldehyde which cannot be described as ~natural". Thus, the use of substances such as hydrogen peroxide and/or sodium hydroxide in the reaction mass would give rise to a material not contemplated within the scope of our invention.

Thus, our invention specifically is intended to exclude processes such as those of the prior art, for example, Reeves, et al, TAPPI, 48(2), 121-5, (1965) which discloses the reaction:

O

t ~ l~z 02 ' U

The reaction of our invention, to wit:
.

~ ~ I

[~ t8~9sE] ~

may be carried out in a standard reaction vessel preferably at reflux conditions (preferably when the cinnamaldehyde-bearing reactant is in the liquid phase, e.g., cinnr ~n oil or cassia oil);
or it may be carried out in solid-liauid phase reaction e~uipment, e.g., ~Soxhlet~-type equipment (preferably when the cinnA~ldehyde-bearing reactant is in the solid phase). Thus, the reaction of our invention may be carried out in a ~Soxhlet" extraction vessel with the actual reaction taking place in the "Soxhlet"
thimble as more specifically described, infra, or the reaction of our invention may be carried out in a "Soxhlet~ extraction vessel with the actual reaction taking place in the reboiler flask or vessel. The case where the reaction takes place in the "Soxhlet" thimble occurs when, for example, pulverized cinn; ~r bark of one of the above types is intimately admixed with lime or magnesium hydroxide or the like and the resulting solid mixture is placed in the "Soxhlet" thimble.

In any case, the reaction may take place in the presence of (i) Cl-C5 alcohols, (ii) water, or (iii) aqueous mixtures of Cl-C5 alcohols and water. Examples of Cl-C5 alcohols are methanol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butanol, secondary butanol, tertiary butanol, n-amyl alcohol, ``
t-amyl alcohol and isobutanol. The weight ratio of alcohol:water when an alcoholic solution is used, may vary, and is preferably from about 6 parts alcohol:4 parts water (by wei~ht) up to about 1 part alcohol:about 10 parts water (by weight).

~ -13-The reaction is carried out at temperatures such that acet-aldehyde and benzaldehyde are removed from the reaction mass as ;they are formed thereby flavoring the "retro-aldol" reaction.
Hence, temperatures substantially greater than the boiling point of acetaldehyde are to be used. The boiling point of acetaldehyde is 21C at atmospheric pressure. Pressures o~ from about 0.2 atmospheres up to about 10 atmospheres may be used in carryin~
;out this reaction. Thus, for example, refluxing water at 1 atmo-sphere gives rise to a reaction temperature of about 90C whereas refluxing 50:50 ethanol:water at atmospheric pressure gives rise to a reaction temperature of about 80C. The reaction temperature may thus vary from about 40C up to about 150C. The reaction pressure may thus vary from about 0.2 atmospheres up to about 10 - atmospheres. The reaction time may vary from about 5 hours up to about 80 hours. The longer the reaction time, the greater the degree of "completion" of the reaction (giving rise to a greater ratio of benzaldehyde:cinnamaldehyde in the final product). The shorter the period of reaction time the higher the temperature required in order to substantially Ncomplete~ the reaction (whereby the weight percent of benzaldehyde in the reaction mass is greater than about 40%).

I Thus, within the meaning of our specification, the term "completion" of reaction means the formation in the reaction ~ mass of at least a 10% yield of "natural" benzaldehyde and a ~- 10% yield of acetaldehyde up to about a 95~ yield of "natural"
benzaldehyde and a 95% yield of Nnatural" acetaldehyde. Carrying out our process in order to yield less than 10% of benzaldehyde ;or acetaldehyde or greater than 95% yield of benzaldehyde or acetaldehyde becomes uneconomical and is not contempiated within the scope of our invention.
,j When using as a source of c;nnAmaldehyde one or both of the compounds having the structures:
1, O

~ and ~

cinni o~ oil or oil of cassia oil, the cinnamon oil or oil of cassia is ad~ixed with water or a Cl-C5 alcohol or a mixture of water and a Cl-C5 lower alkanol as well as the base, e.~., sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, lithium carbonate, lithium bicarbonate, calcium hydroxide, calcium carbonate, magnesium hydroxide, magnesium carbonate, proline having the structure:

O
~OH

choline having the structure:

[O H]

f~O J

f ~

or a lecithin-base mixture with the lecithin having the structure:

rH2 - 0~ - R
O
CH - O - C - R' CH2 O _ I! O CH2 - CH2 - N - CH3 1 a CH3 wherein the moieties:

// and //
~\ ' C~
R `~
~ , ~ ~

are defined, supra, the reaction mixture is then refluxed or heated for a period of between about 5 hours and about 8~ hours.
During the reaction, it is desirable to remove the benzal-dehyde-rich reaction product as it is formed. Hence, the benzaldehyde-rich reaction product may be removed overhead through a packed vertical reflux column connected to a cooling heat exchanger as illustrated in Figures 7A, 7B or 7C, infra.
The product thus obtained exists in two phases; an upper aqueous phase and a lower more dense benzaldehyde-rich phase which can be separated from each other using a phase splitters or the benzaldehyde-rich phase is separated from the aaueous phase, for example, by solvent extraction using such solvents as diethyl ether, dimethyl ether, hydrocarbons or methylene dichloride, and the benzaldehyde-rich phase may then be fractionally distilled. The acetaldehyde may be separated from the benzal-dehyde by means of the use of a high efficiency fractionation column and cooling heat exchanger. As will be seen in Figure 7A, the acetaldehyde may be separated by trapping said acetaldehyde in a n cold trap".

, ~

Thus, at the end of the reaction or at the end of the desired time period for proceeding with the reaction, the "natural"
benzaldehyde~and "natural" acetaldehvde are fractionally distilled yielding mixtures rich in natural benzaldehyde and/or acetaldehyde.
The benzaldehyde-rich fraction also may contain a considerable proportion of unreacted cinnamaldehyde. This resulting product may, if desired, be again fractionally distilled in order to enrich the benzaldehyde stream. From a practical standpoint such a mixture of cinnamaldehyde and benzaldehyde produced accordina to the first fractional distillation is usually adequate for use in food flavors, for example, or in tobacco flavors, for example.

Normally, but not necessarily, the acetaldehyde is prepared free of aro~atic aldehydeq for use in food flavors.

From a practical standpoint, the mixtures of acetaldehyde, benzaldehyde and cinnA~aldehyde thus produced have unobvious, unexpected and advantageous properties for augmenting or enhancing the aroma or taste of consumable materials includin~ but not limited to foodstuffq, chewing gums, medicinal products, tooth-pastes, chewing tobaccos, smoking tobacco and smoking tobacco articles, particularly almond, orange and cherry flavored food-stuffs and medicinal products.

The range of mole ratio of base to cinnamaldehyde (contained in the c;nnA~ldehyde-Dearinq natural substance, e.g., cassia oil, ci nni ~ bark, cinnamon leaf and the like) may vary from about 0.1:1 up to about 4:1. This mole ratio is based upon the following:

(a) Whether the reaction is carried out on a solid containing the cinnamaldehyde such as pulverized cinnamon bark or in admixture with a base such as magnesium hydroxide (in which case the higher end of the range of mole ratios is applicable);
or whether the reaction is a liquid phase reaction carried out in the presence of a base such as choline, proline or aqueous sodium bicarbonate with cinnA~Qn oil and water, alcohol or an aaueous alcohol mixture (in which case the mole ratio of base:cinnamaldehyde is at the lower end of the above-mentioned range;

i (b) The nature of the total ener~y input to the reaction;
ba$ed upon heat input and time of reaction as well as temperature and pressure of reaction (thus, a relatively long time of reaction, e.g., 80 hours, will give rise to a higher ~yield" of benzaldehyde and acetaldehyde and a lower concentration of cinnamaldehyde in the reaction product). Depending upon the flavorist's requirements, it may be desirable to create an ultimate composition containing, for example, greater than 80% benzaldehyde or a 50:50 mixture of benzaldehyde and cinnamaldehyde or substantially pure acetaldehyde (having present therewith minor quantities of other low boiling components such as crotonaldehyde and acetic acid); and (c) The particle size (where applicable) of the solid source of c jnni -ldehyde, e.g., pulverized cinnamon bark or pulverized high cinnamaldehyde-containing cinni- -n leaf. A small particle size will give rise to a faster conversion of cinnamaldehyde (contained in the solid cinnamaldehyde-bearing source) to benzaldehyde and acetaldehyde.

In all cases, our invention is capable of yielding in a controll-able fashion desired ratios of benzaldehyde and acetaldehyde to cinnamaldehyde depending upon the reaction conditions employed.

~ he reaction product containing the cinni ~ldehyde, benzaldehyde and acetaldehyde produced according to the reaction:

~ l~fiSE~

~' l i i I, 1 3 3 6 1 2 7 may be considered as a "natural" product, This "natural" product may be used ~as is~ or it may preferably be physically purified by such meth~ds as fractional distillation and/or preparative chromatography. The resulting ~atural~ products will have novel utilities in au~menting or enhancinn the aroma or taste of consumable materials including but not limited to foodstuffs, chewing gums, medicinal product~, toothpastes, chewing tobaccos and smoking tobaccos particularly cherry flavored, orange fla~ored, almond flavored foodstuffs and medicinal products.
Accordingly, for example, compositions of matter containing mole ratios of from about 10:90 up to about 99.9:0.1 of benzal-dehyde:cinnamaldehyde in their natural state prepared according to the reaction:

+ o > ~11+ lh may be utilized in such consumable materials, e.g., foodstuffs as, for example, macaroon cookies, maraschino cherries, cherry flavored be~erages such as carbonated cherry drinks, and the like.

Furthermore, substantially pure acetaldehyde containing minor amounts of impurities may be utilized in such consumable materials, e.g., foodstuffs such as oranqe drinks.

. I .

- i,,, ~

., --19--Collectively, these aforementioned benzaldehyde, cinnamal-dehyde and acetaldehyde-containing products of our invention are hereinafter called "aldehyde-containing compositions".

The novel products of our invention may be utilized in foodstuffs and be~erages in an amount of from about 0.5 ppm up to about 3~ by weight of the resulting foodstuff or beverage.
The materials can be used in such high percentages because of the manner in which they are produced; that is, free of any nitrile-containing substances as would be present if the aldehyde-containing products were produced from such materials as apricot kernels.

As used herein, the term "foodstuff" includes both solid and liquid ingestible materials which usually do, but need not, have nutritional value. Thus, foodstuffs includes soups, convenience foods, beverages, dairy products, candies, vegetable cereals, soft drinks, snacks and the like.

As used herein, the term "medicinal products" includes both solids and liquid~ which are ingestible non-toxic materials which have medicinal value such as cough syrups, 'cough drops and chewing medicinal tablets.

, The term "chewing gum" is intended herein to be a foodstuff composition comprising a substantially water-insoluble, chewable plastic gum base such as chicle, or substitutes therefor, including jelutong, guttakay rubber or certain comestible natural or synthetic resins or waxes. Incorporated I with the gum base in admixture therewith may be plasticizers or ! softening agents, e.g., glycerine and a flavoring composition j which incorporates one or more of the aldehyde-containing co~positionsof our in~ention and, in addition, sweetenlng agents which may be sugars, including sucrose or dextrose and/or artificial sweeteners suc~ as cyclamates or saccharin. Other optional ingredients may be present.

., .

The term "augment" in its various forms is used herein to mean the supplying, modifying or imparting of a flavor or aroma characteristi~c note or nuance to an otherwise bland, relatively tasteless or non-odorous substance or modifying an existing flavor or aroma characteristic where the natural flavor is deficient in some regard, or supplementing the existing flavor or aroma impression to modify its quality, character, taste or aroma.
, The term "enhance" is used herein to mean the intensification of a flavor or aroma characteristic or note without the modifi-cation of the quality thereof. Thus, ~enhancement" of a flavor or aroma means that the enhancement agent does not add any additional flavor note or nuance.

Substances suitable for use herein as co-ingredients or flavoring adjuvants are well known in the art for such use, being extensively described in the relevant literature. It is required that any such material be "ingestibly acceptable" and thus non-toxic or otherwise non-deleterious, particularly from an organoleptic standpoint whereby the ultimate flavor and/or aroma of the consumable material used does not cause the consumable material to have unacceptable aroma and taste nuances.

-~ It is a further requirement that such material be organoleptically compatible with the foodstuff with which it is used so that the flavor and aroma nuances of such material, taken together with the flavor and aroma nuances of the foodstuff (as a whole) give rise to a harmoniously aesthetically pleasing aroma and taste profile. Such material, in general, may be characterized as flavoring adjuvants or vehicles comprising broadly, stabilizers, thickeners, surface active agents, conditioners, otner flavorants and flavor intensifiers.

Stabilizer compounds include preservatives, e.g., sodium chloride: antioxidants, e.g., calcium and sodium ascorbate, ascorbic acid, butylated hydroxyanisole (mixture of 2- and 3-tertiary-butyl-4-hydroxyanisole), butylated hydroxy toluene (2,6-di-tertiary-butyl-4-methyl phenol), propyl gallate and the like and sequestrants, e.g., citric acid.

Thickener compounds include carriers, binders, protective colloids, ~uspending agents, emulsifiers and the like, e.g., agar agar, carrageenan, cellulose and cellulose derivatives such as carboxymethyl cellulose and methyl cellulose; natural and synthetic gums such as gum arabic, gum tragacanth, gelatin, proteinaceous materials; lipids, carbohydrates;
starches,pectins and emulsif,iers, e.g., mono- and diglycerides of fatty acids, skim milk powder, hexoses, pentoses, disaccharide~, e.g., ~ucrose, corn syrup and the like.

Surface active agents include emulsifying agents, e.g., fatty acids such as capric acid, caprylic acid, palmitic acid, myristic acid and the like, mono- and diglycerides of fatty acids, lecithin, defoaming and flavor dispersing agents such as sorbitan monostearate, potas~ium stearate, hydrogenated tallow alcohol and the liXe.

Conditioners include compounds such a~ bleaching and maturing agents, e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and the like, starch modifiers such as peracetic acid, sodium chlorite, sodium hypochlorite, propylene oxide, succinic anhydride and the like, buffers and neutralizing agents, e.g., sodium acetate ammonium bicarbonate, ammonium phosphate, citric acid, lactic acid, vinegar and the ,~ jlike, colorants, e.g., carminic acid, cochineal, tumeric and curcumin and the like, firming agents such as aluminum sodium sulfate, calcium chloride and calcium glyconate, texturizers, anti-caking agents, e.g., aluminum calcium sulfate and tribasic calcium phosphate, enzymes, yeast foods, e.g., calcium lactate and calcium sulfate, nutrient supplements, e.g., iron salts such as ferric phosphate, ferrous gluconate and the like, riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfate and the like.

Other flavorants and flavor intensifiers include organic acids, e.g., acetic acid, formic acid, 2-hexenoic acid, benzoic acid, n-butyric acid, caproic acid, caprylic acid, cinnamic acid, isobutyric acid, isovaleric acid, alpha-methyl-butyric acid, propionic acid, valeric acid, 2-methyl-2-pentenoic acid, - j ~
!

i 1 336 1 27 and 2-methyl-cis-3-pentenoic acid: ketones and aldehydes other than the aldehydes of the aldehyde-containing compositions of our invention, e~g., acetophenone~ acetone~-acet~1 methyl carbinol, acrolein, n-butanal, crotonal, diacetyl, beta,beta-dimethyl-acrolein, n-hexanal, 2-hexanal, cis-3-hexenal, 2-heptenal, 4-(p-hydroxyphenyl)-2-butanone, alpha-ionone, beta-ionone, 2.methyl-3-butanone, 2-pentanone, -pentenal and propanal; alcohols such as l-butanol, benzyl alcohol, l-borneol, trans-2-buten-1-ol, ethanol, geraniol, l-hexanol, 2-heptanol, trans-2-hexenol-1, cis-3-hexen-1-ol, 3-methyl-3-buten-1-ol, l-pentenol, 1-penten-3-ol, p-hydroxy-phenyl-2-ethanol, isoamyl alcohol, isofenchyl alcohol, phenyl-2-ethanol, alpha-terpineol, cis-terpineol hydrate, esters, such as butyl acetate ethyl acetate, ethyl aceto-acetate; ethyl benzoate, ethyl butyrate, ethyl cinnamate, ethyl crotonate, ethyl formate, ethyl isobutyrate, ethyl isovalerate, ethyl alpha-methyl-butyrate, ethyl propionate, ethyl sali-cylate, trans-2-hexenyl acetate, hexyl acetate, 2-hexenyl butyrate, hexyl butyrate, isoamyl acetate, isopropyl butyrate, methyl acetate, methyl butyrate, methyl caproate, methyl isobutyrate, methyl-2-methyl-butyrate, propyl acetate, amyl acetate, amyl butyrate, benzyl salicylate, dimethyl anthran-ilate, ethyl methylphenylglycidate ethyl succinate isobutyl cinnamate and terpenyl acetate; essential oils such as jasmin absolute, rose absolute, orris absolute, lemon essential oil, Bulgarian rose, yara yara, natural raspberry oil and vanilla;
lactones, sulfides, e.g., methyl sulfide and other materials such as maltol, acetoin and acetals (e.g., l,l-diethoxyethane, l,l-dimethoxyethane and dimethoxymethane~ ~-The specific flavoring adjuvant selected for use may beeither solid or liquid depending upon the desired physical form of the ultimate product, i.e., foodstuff, whether simulated or natural, and should, in any event, be capable of providing an environment in which the cyclic chemical compounds can be dispersed or admixed to provide a homogeneous medium. In addition, selection of one or more flavoring adjuvants, as well as the quantities thereof will depend upon the precise organoleptic character desired in the finished product. Thus, in the case of flavoring compositions, ingredient selection ;will vary in accordance with the foodstuff to which the flavor and aroma are,to be imparted. In contradistinction, in the preparation of solid products, e.g., simulated foodstuffs, ingredients capable of providing normally solid compo6itions .
should be ~elected such as various cellulose derivatives.

As will be appreciated by those skilled in the art, the -amount of aldehyde-containing composition of our invention employed in a particular instance can vary over a relatively wide range whereby its desired organoleptic effects (having reference to the nature of the product) are achieved. Thus, correspondingly greater amounts would be necessary in those instances wherein the ultimate food composition to be flavored is relatively bland to the taste, whereas relatively minor quantities may suffice for purposes of enhancing the composition merely deficient in natural flavor or aroma. The primary requirement is that the amount selected (to be effective) be sufficient to augment or enhance the organoleptic characteristics of the parent composition (whether foodstuff per se or flavoring composition).

The use of insufficient quantities of aldehyde-containing composition of our invention, will, of course, substantially vitiate any possibility of obtainlng the desired results while excess quantities prove needlessly costly and in extreme cases, may disrupt the flavor-aroma balance, thus proving self-defeating.
Accordingly, the terminology "effective amount" and ~sufficient amount" is to be accorded a significance in the context of the present invention consistent with the obtention of desired flavoring effects.

Thus, and with respect to ultimate food composition, it is ~found that quantities of aldehyde-ccntaining composition of our invention ranging from a small but effective amount, e,g., 0.5 ppm up to 3% by weight based on total composition are suitable as stated, supra. Concentrations in excess of the maximum quantity stated are not normally recommended, since f they fail to provide cl ~nsurate enhancement of organoleptic properties. ,In those instances where the aldehyde-containing composition of our invention is added to the foodstuff as an integral component of a flavoring composition, it is, of course, essential that the total quantity of flavoring composition employed be sufficient to yi~ld an effective amount of aldehyde-containing composition.

Food flavoring compositions prepared in accordance with the present invention preferably contain the aldehyde-containing composition of our invention ranging from about 0.1~ up to about 100% by weight based on the total weight of said flavorin~
composition.

The compositions described herein can be prepared according to conventional techniques well known as typified by cake batters and fruit drinks and can be formulated by merely admixing the involved ingredients within the proportions stated in a suitable blender to obtain the desired consistency, homogeneity of dispersion, etc. Alternatively, flavoring compositions in the form of particulate solids can be convenlently prepared by mixing the aldehyde-containing composition of our invention with, for example, ~um arabic, gum tragacanth, carrageenan and the like, and thereafter spray-drying the resultant mixture whereby to obtain the particulate solid product. Pre-prepared flavor mixes in powder form, e.g., a fruit flavored powdered mix, are obtained by mixing the dried solid components, e.g., starch, sugar and the like and aldehyde-containing composition in a dry blender until the requisite degree of uniformity is achieved.
. ~
The novel aldehyde composition-containing substances produced according to the novel process of our invention may be used "as is" as stated, supra, or may be used in con~unction with other flavor adjuvants including but not limited to:

, .' !

Heliotropin~
Terpinenol-4;
Anisaldehyde;
Phenyl acètaldehyde;
Benzyl formate;
Benzyl acetate;
Cis-3-hexenyl benzoate:
Methyl Hexanoate;
Hexanal;
Eucalyptol, Eugenol;
Ethyl acetate;
Ethyl butyrate;
Turpentine gum oil;
Limonene;
Gum camphor:
Isobornyl acetate;
Borneol;
Cuminic aldehyde;
Furfural;
Methyl cinnamate;
Cassia oil;
Vanillin;
Maltol;
Parahydroxybenzylacetone;
Dimethyl ~ulfide;
Alpha-ionone;
Acetic acid;
Isobutyl acetate;
Acetone;
Butyric acid;
Formic acid;
Valeric acid;
Amyl acetate;
Amyl butyrate;
Anethol.
Benzyl salicylate;
Diacetyl;
Dimethyl anthranilate;
Ethyl methylphenylglycidate, t 33 6 1 27 ~thyl succinate;
Ethyl valerate;
Geraniol, Cis-3-hexen-1-ol;

2-Hexenyl acetate;
2-Hexenyl butyrate;
Hexyl butyrate;
4-(p-Hydroxyphenyl)-2-butanone:
Beta-ionone;
Isobutyl cinnamate;
Jasmine;
Lemon essential oil;
Methyl butyrate:
Methyl capronate;
Methyl disulfide;
Methyl p-naphthyl ketone;
Orri~ butter;
Ro~e absolute;
Terpenyl acetate;
Gamma-undecalactone;
Vanilla;
Alcohol;
Oil of Cubeb;
Phellandrene;
Beta-phellandrene;
Oil of Coriander;
Oil of-Pimento Leaf;
Oil of Patchouli;
Alpha-Pinene;
Beta-Pinene;
Beta-caryophyllene;
Dihydrocarveol;
Piperonal;
Piperine;
Chavicine;
Piperidine;

c l ~

Oil of 31ack Pepper;
Black Pepper Oleoresin;
Caps icum, Oil of Nutmeg;
Cardamon Oil;
Clove Oil;
SpeA ; nt Oil; and Oil of Peppermint.

An additional aspect of our invention provides an organo-leptically improved smoking tobacco product and additives therefor, as well as methods of making the same which overcome specific problems heretofore encountered in which specific desired sweet and fruity flavor characteristics of natural tobacco are created or enhanced and may be readily controlled and maintained at the desired uniform level regardless of variations in the tobacco components of the blend.

This invention further provides improved tobacco additives and methods whereby variouæ desirable sweet and fruity flavoring characteristics may be imparted to smoking tobacco products and may be readily varied and controlled to produce the desired uniform flavoring characteristics.

In carrying out this aspect of our invention, we add to smoking tobacco materials or a suitable substitute therefor (e.g., dried lettuce leaves) or we add to filters for smoking ~tobacco articles (e.g., cellulose acetate filters) an aroma and flavor additive containing as an active ingredient the aldehyde-contA~n~ng composition of our invention which ls the benzaldehyde/c1nni ~ldehyde composition.

In addition to the benzaldehyde/cinnamaldehyde composition of our invention other flavoring and aroma additives may be added to the smoking tobacco material or substituted therefor either separately or in admixture with the benzaldehyde/cinna-maldehyde composition of our invention as follows:

I. SYNTHETIC MATERIALS

Beta-ethyl-cinnamaldehyde:
Eugenol;
Dipentene;
Beta-Damascenone;
Maltol;
Ethyl maltol;
Delta undecalactone;
Delta decalactone;
Amyl acetate:
Ethyl butyrate;
Ethyl valerate:
I Ethyl acetate;
:! 2-Hexenol;
1,2-Methyl-5-isopropyl-1,3-nonadiene-8-one;
2,6-Dimethyl-2,6-undecadiene-10-one;
2-Methyl-5-isopropyl acetophenone;
2-Hydroxy-2,5,5,8a-tetramethyl-1-(2-hydroxyethyl)-decahydronaphthalene;
Dodecahydro-3a,6,6,9a-tetramethyl naptho-[2,1-b]-furan;
4-Hydroxy hexanoic acid, gamma lactone;
Polyisoprenoid hydrocarbons defined in Example V of U.S. Patent No. 3,589,372 issued on June 29, 1971.

II. NATURAL OILS
Celery iseed oil;
Coffee extract;
Bergamot Oil;
Cocoa extract;

Nutmeg oil:
Origanum oil;

.''i An aroma and flavoring concentrate containing the benzal-dehyde/cinnamaldehyde composition of our invention and, if ,desired, one~or more of the above indicated additional flavor-ing materials may be added to the smoking tobacco material, to the filter or to the leaf or paper wrapper. The smoking tobacco material may be shredded, cured, cased and blended tobacco material or reconsti~uted tobacco material or tobacco -cubstitutents (e.g., lettuce leaves) or mixtures thereof. The proportions of flavoring additives may be varied in accordance with taste but insofar as enhancement or the imparting of natural and/or sweet notes, we have found that satisfactory results are obtained if the proportion by weight of the sum total of the benzaldehyde/cinnamaldehyde composition of our invention to smoking tobacco material i8 between S and 100 ppm (0.0005-0.01%) of the active ingredients to the smoking tobacco material. We have further found that satisfactory results are obtained if the proportion by weight of the sum total of benzaldehyde/cinnamaldehyde composition of our invention used to flavoring material is between 50 and 1000 ppm (0.005-0.1%).

Any convenient method for incorporating the benzal-dehyde/cinnamaldehyde composition of our invention in the tobacco product may be employed. Thus, the benzal-dehyde/cinnamaldehyde composition of our invention taken alone ; or along with other flavoring additives may be dissolved in a suitable solvent such as ethanol, pentane, diethyl ether and~or other volatile organic solvents and the resulting solution may either be spread on the cured, cased and blended tobacco material or the tobacco material may be dipped into such solution. Under certain circumstances, a solution of the benzaldehyde/cinnamaldehyde composition of our invention taken alone or taken further together with other flavoring additives as set forth above, may be applied by means of a suitable ! applicator such as a brush or roller on the paper or leaf wrapper for the smoking product, or it may be applied to the - ;filter by either spraying, or dipping or coating.

Furthermore, it will be apparent that only a portion of the tobacco or substituted therefor need be treated and the thus treated tobacco may be blended with other tobaccos before the ultimate tobacco product is formed.

~ l !
; In such cases, the tobacco treated may have the benzaldehyde/cinnamaldehyde composition of our invention in excess of the`amounts or concentrations above indicated so that when blended with other tobaccos, the final product will have the percentage within the indicated range.

In accordance with one specific example of our invention, ; an aged, cured and shredded domestic burley tobacco is spread with a 20% ethyl alcohol solution of a mixture containing 75~
benzaldehyde and 25~ cinnamaldehyde prepared by carrying out a ~reaction in a "Soxhlet" apparatus of the type set forth in Figure 4 using an Mg(OH)2 catalyst. The amount of benzaldehyde/cinnamaldehyde composition is 20 ppm on a dry basis. Thereafter, the alcohol is removed by evaporation and the tobacco is manufactured into cigarettes by the usual techniques. The cigarette when treated as indicated has a desired and pleasing sweet and fruity aroma with faint aesthetically pleasing cherry nuances which is detectable in the main and side streams when the cigarette is s ked. The aroma is described as being sweeter~ rich~ less harsh~ more tobacco-like and having fruity notes.

While our invention is particularly useful in the manufacture of ~moking tobacco, such as cigarette tobacco, cigar tobacco and pipe tobacco, other tobacco products formed from sheeted tobacco dust or fines may also be used. Likewise, the benzaldehyde/cinnar-ldehyde compositions of our invention can be incorporated with materials such as filter tip materials, seam paste, packaging materials and the like which are used along with tobacco to form a product adapted for smoking. Furthermore, the benzaldehyde/cinnamaldehyde compositions of our invention can be added to certain tobacco substitutes of natural or synthetic origin (e.g., dried lettuce leaves) and, accordingly, by the term "tobacco" as used throughout this specification is meant any composition intended for human con~umption by smoking or otherwise. whether composed of tobacco plant parts or substitute materials or both.

, .
BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 is the GC-IR spectrum for the reaction product of Example I containing benzaldehyde and cinnamaldehyde.

Figure 2 is a GC-IR spectrum for the distillation residue of Example I containing cinnamaldehyde and benzaldehyde.

Figure 3 is a GC-IR spectrum for the reaction product of Example II containing benzaldehyde and cinnamaldehyde (Conditions: Carbowax column programmed at 7S-225~C at 3C per ~inute~.

Figure 4 is a cut-away cross sectional elevation view of a Soxh;et apparatus used for carrying out the reaction:

~ ~.

~ tE~SE]> ~ 1 when the cin~a~-ldehyde is present in a solid material such as pulverized cinna~on bark and when the basic catalyst is a solid such as ~agnesium hydroxide or calcium hydroxide.

i l *Trade Mark il 1336127 Figure 5 is a simplified Soxhlet reaction apparatus fitting for carrying out the reactions ~ tB-9~E]

~ ^ ~
-- . 1 3361 27 ! 33 : Figure 6 is a diagram of a solid-liquid phase reaction apparatus useful in carryiny out the retro-aldol reaction, to wit:

~ t8~9~']> ~ 1 when the cinnamaldehyde having the structure:

~0 o or a mixture thereof is in existence in a natural solid .material such as cinnamon bark.

Figure 7A`is a diagram of a liquid-liquid phase reaction and recovery apparatus for carrying out the reaction:

~ tB~9X]~

and recovering the natural benzaldehyde-containinq composition and the natural acetaldehyde-containing composition of our ~invention (as employed iD Example VI, infra).

Figure 7B is a diagram of a section of the apparatus of Figure 7A showing the magnetic coil-actuated recovery-return mechanis~ of the apparatus useful in the practice of our invention.

. 13~6127 Figure 7C is a diagram of a continuous liquid-liauid phase reaction-recovery apparatus for carrying the reaction:
!
~ .

t l ~

and recovering the natural benzaldehyde-containing composition and natural acetaldehyde-containing composition of our invention.

Figure 8 i8 the GLC profile of the reaction product produced according to Example VI containing benzaldehyde and cinnamaldehyde.

Figure 9 is the GLC profile of a first distillation product of the reaction product of Example VI rich in benzaldehyde.

Figure 10 is the GLC profile of a second distillation product of the reaction product of Example VI rich in benzaldehyde.

Figure 11 is the GLC profile of a third distillation product of the reaction product of Example VI rich in benzaldehyde.

Figure 12 is a total ion current spectrum of a GC-MS analysis of acetaldehyde-rich product recovered in cold trap 231 of the apparatus of Pigure 7A.

1 3~61 27 DETAILED DESCRIPTION OF THE DRAWINGS

Figure 1 is the GC-IR spectrum for the crude reaction product of Example I. The peak indicated by reference numeral 10 is the peak for benzaldehyde in the reaction product. The peak indicated by reference numeral 11 i8 the peak for cinna-maldehyde having the structures:

.

~ ~nd ~ ~

!
Figure 2 is the GC-IR spectrum for the distil'lation residue of Example I containing benzaldehyde and cinnamaldehyde. The ;peak indicated by reference numeral 20 is the peak for benzal-dehyde. The peak indicated by reference numeral 21 is the peak for the unreacted cin~ ldehyde having the structure:
o ~ and ~

Figure 3 is the GC-IR spectrum for the crude reaction product of Example II. The peak indicated by reference numeral 30 is the peak for benzaldehyde. The peak indicated by reference numeral 31 is the peak for cinnamaldehyde.

11 ~
, . - , !

,.,~ i -_37_ 1 336 1 27 .

The apparatus of Figure 4 (the Soxhlet reaction apparatus) ~is used to effect the reaction: !

~o ~

when the cinnamaldehyde is present in such solid materials as pulverized cinnamon bark. .~.

The mixture of cinnamaldehyde-bearing material (e.g., pulverzied cinna ~n bark ceylon) and solid natural base, (for example, limestone or lecithin) 46 is placed in a porous thimble 45 (the thus-filled porous thimble is placed in the inner tube 42 of the Soxhlet apparatus). The apparatus is then fitted to a bolt-head flask 41 containing water, a Cl-C5 alkanol or a mixture of water and a Cl-C5 lower alkanol, e,g., methanol, ethanol, isopropanol, n-propar.ol, n-butanol, isobutanol, t-butanol, t-amyl alc~hol or n-amyl a1cohol and to reflux condenser 57 having a cooling jacket 54 fitted with cooling liguid inlet tube 55 surrounding a condenser surface 53. The reflux condenser havinq outlet 56 is tightly fitted via stopper 52 to the inner tube 42 of the ~Saxhlet~ apparatus. The solvent, the water, the alkanol Dr the water-alkanol mixture is boiled at location 40 in flask 41.
The vapor passes up through the tube 44 and is condensed by condenser 57 and the condensed solvent falls from ~53 through opening 56 into the thimble 45 and slowly fills thè body of the apparatus 47. When the water or Cl-C5 alkanol or the water Cl-C5 ~ower alkanol mixture contacts the mixture of pulverized cinnamal-dehyde-bearing material and solid base (e.g., Mg(OH)2 in thimble 45, a retro-aldol reaction is effected, thusly:

~ { ~ ~

. -38-~ r ~ ~ 1 , The result of this reaction is the formation of a water-cinnamaldehyde-benzaldehyde-acetaldehyde mixture or a water-cinn; aldehyde-benzaldehyde-acetaldehyde Cl-C5 lower alkanol mi~ture. The solid-liquid reaction mass residence time in the thimble must be sufficient to allow a final yield of benzaldehyde and acetaldehyde in amounts of 10% or more.

When the mixture reaches the top of tube 43 , it siphons over through tube 43 into flask 41 and thus effects removal of ~that portion of the reaction product which is "extracted" in thimble 45. The process i~ repeated automatically as the reaction proceeds in thimble 45, that is, the retro-aldol reaction, to wit:

~ r ,E~

~ J

proceeds in thimble _ . The resulting "natural" benzaldehyde ~ay be isolated as by fractional distillation.

In place of the solid base, e.g., Hq(OH)2 at location 46, a lecithin-base mixture (lecithin is a chloline precursor having the structure:
!

~H2 - - R
O

CH - O - ~ - R' 1 ~ CH3 ~H2 ~ - - O - ~H2 - CH2 - N - CH3 ~a ~H3 wherein the moietie~:

/ O and / O
~ ~\ C\
R ,p, ha~e been defined, supra) may be added at location 40 ~ith the reaction ta~ing place at location 40 rather than at location 46 or a natural proline or choline embedded in an inert polymer haYing micropores such as microporous polyethylene may be admixed with the cinnamaldehyde-bearing solid, e.g., the pulverized clnn~o~ bark at location 46.

In the case of the reaction taking place at location 46, the siphone tube 43 has an outlet into the flask 41 at 51 wherein the reaction product containing large amounts of ben-zaldehyde together with water, alkanol or water/alkanol mixture is passed through the opening 51 of siphon tube 43 and then through the opening of the Soxhlet apparatus into flask 41.

, The Soxhlet apparatus is firmly in place in a vapor-tiqht manner as a result of the placement of tube 49 in tiahtly-fitting stopper 48 located in the neck of flask 41 at location 50.

In the case of the reaction taking place at location 41, the siphon tube 43 has an outlet into the flask 41 at 51 wherein !I extracted cinnamaldehyde together with water, alkanol or !water/alkanol mixture is passed through the opening 51 of siphon tube 43 and then through the opening of the Soxhlet apparatus into flask 41. The Soxhlet apparatus is firmly in place in a vapor-tight manner as a result of the placement of tube 49 in tightly-fitting stopper 48 located in the neck of flask 41 at location -50.

In place of Soxhlet apparatus and tube 42, the retro-aldol reaction can take place in an apparatus of the nature of Figure 5.

Referring now to Figure 5, the solid cinnamaldehyde-con-taining material, for example, pulverized cinnamon bark may be placed on a sintered glass disc 70 of Figure 5 and the entire apparatus may be fitted onto a reaction vessel which is also fitted with a distillation apparatus~ Hot Cl-C5 alkanol or hot alkanol-water mixture or hot water may be added through , opening 73 into tube 71 slowly passedthe pul~erized cinnmal-dehyde-containing material resting on sintered alass disc 70.
The water, Cl-C5 alkanol or the water/Cl-C5 lower alkanol ! mixture may be admixed with a base such as proline, choline, sodium bicarbonate~ potassium bicarbonate, sodium carbonate, sodium bicarbonate, lithium carbonate or lithium bicarbonate or a mixture of lecithin and base. In the alternative, the cinn~ ~ldehyde-yielding material may be admixed with solid , base (e.g., Mg(OH)2 or Ca(OH)2) while restina on sintered glass j disc 70. The entire apparatus is fitted at 72 into a flask haYing fitted thereto a di~tillation apparatus. As the benzaldehyde-rich and acetaldehyde-rich reaction mixture passes through disc 70 through opening 74 into the flask it may be simultaneously distilled or it may be recycyled if it contains an excessive amount of cinnamaldehyde that has not reacted and if it is desired to create e more enriched benzaldehyde-cont-aining product.

:

Figure 6 is a schematic diagram of a isolid-liauid phase reaction apparatus which can be used to carry out the retro-aldol reaction of our invention, to wit:

~o O
~ ~8 Set forth in Figure 6 is a solid-liquid retro-aldol ~- -~
reaction apparatus which is specifically described in United !States Lettes Patent No. 1,636,550~
: . ,Specifically, in Figure 6, the numeral 2001 designates a holder for particular~zed - cinnamaldehyde-bearing solid, for example, particularized cin~a -- bark or cinna n~ leaf which contains a large quantity of cinnamaldehyde having the structures:
.

G

~0 ~

ç

i .

taken alone o`r mixed with a solid basic catalyst (e.g., Ca(OH)2 or Mg(OH)2 which is shown at 2002 in the drawin~s. Arranged below the holder is a vaporizing apparatus for reaction solvent, ~e.g., water a Cl-C5 lower alkanol or a mixture of Cl-C5 lower 'lalkanol and water (such as a 50:50 mixture of ethanol and water, which apparatus consists preferably of a closed container 2003 arranged in a heating bath vessel Z004 whlch may be a hot oil bath. Heat may be applied to vessel 2004 either by gas flame, steam coils located in the vessel, solar energy or any other suitable means. Connected with the holder 2001 is a condenser 2005. The condenser 2005 may be of an~ suitable construction. It is shown as consisting of a vessel provided with two interior headers 2006 and 2007 having a plurality of condensing tubes 2008. The space between the headers is supplied with a cooling fluid by means, for example, of a cold water inlet pipe 2009. 2010 is an outlet pipe for coolinq fluid which fluid may, if desired, be artifically cooled before beinq introduced into the condenser to the extent necessary to completely condense the vaporized solvent to a temoerature of 60-80C, for example, although this temperature will necessarily vary with the pressure in the holder.

Reference numeral 2011 indicates a pipe for conductin~ the vaporfzed water of lower alkanol or mixture of water and lower al~anol from ve~sel 2003 into the upper portion of the holder 2001. Reference numeral 2012 indicates a pipe leading from the lower portion of the holder to the vessel 2003, preferably. It i i9 desirable to form pipe 2-012 with an upward bend 2013 whereby I the water or lower alkanol or mixture of water and lower alkanol j will be accumulated in the holder to a certain level, that is to say, above the body of reaction mass, that is, the pulverized c~nn; -ldehyde-bearing solid materials such as pulverized cinnamon bark Ceylon intimately admixed with solid basic catalyst, e~g., Mg(OH)2 or Ca(OH)2 before beinq discharged to vessel 2003.
When the outflow from the holder is started, it is continued siphon~cally until the holder is emptied of liquid so that the action is intermittent. The solid-liauid reaction mass residence time in the thimble must be sufficient to allow a final yield of benzaldehyde and acetaldehyde in a~ounts of 10% or more.

~i t , An evacuating mechanism is provided for maintaining a constant I sub-atmospheric pressure in the holder, condenser and vaporizing i vessel 2003. For example, a vacuum pump 2014 may be connected by pipe 2015 to the top of the condenser 2005. The method of the retro-aldol reaction applied to the treatment of the cinnamaldehyde-bearing solid, e.g., pulverized cinn~ -n bark or pulverized cinn ~n leaf, and using the apparatus as above described is as follows:

The pulverized cinnamaldehyde-bearing solid, e.g., cinnamon bark Ceylon is comminuted and placed in the holder 2001. At a 1:1 mole ratio (for example) the solid basic catalyst, e.g., Mg(OH)2 or MgO or CaO or Ca(OH)2 is added to the pulverized cinnamaldehyde-bearing material (the mole ratio is based on the cinnamaldehyde determined to be in the pulverized cinnamaldehyde-bearing material) and allowed to stand under water, alcohol or an aqueous alcohol mixture such as a 50:50 mixture of ethyl alcohol and water for a period of time (e.g., 30-40 hours).
The water, alkanol or aqueous alcohol mixture may be used in an amount approximating 40-60~ by volume of the pulverized cinn~ ~lAehyde-bearing material, e.g., cinnamon bark Ceylon.

After the pulverized cinnamaldehyde-bearing solid, e.q., c~nn. cn bark hag been macerated, in this Anner, as long as necess~ry, a volume of water, alcohol or aqueous alcohol, e.g., 50:50 ethanol:water preferably equal to at least the volumetric contents of the holder 2001 is placed in vessel 2003 and the water or alcohol-water mixture in vessel 2004 is heated to a temperature in the range of 80-100C (e.g., 85C, for example, when a 50:50 mixture of ethanol and water is present) to bring about vaporization of the alcohol mixture. At the same time, the vacuum pump 2014 is started. The pump may be operated so as to maintain a constant vacuum in the apparatus of from approxi-mately 250 mm/Hg pressure up to approximately 750 mm/Hg pressure.

The vaporized solvent passes from vessel 2003 through pipe !~ 2011-into the ~pace 2016 above the material 2002 in holder and into the conden~er 2005. ColDing in contact with the water li cooled tubes 2008, the vapor is condensed and i8 refluxed upon '! the pulverized cinnamaldehyde-bearing material (e.g., cinnamon bark) treated. As ~oon as the~level of the liquid in the holder ri~es above the upper bend of siphon 2013, the solvent admixed with benzaldehyde~acetaldehyde and cinnamaldehyde is drawn from the bottom of the holder and discharged into vessel2003 , by the siphoning action described. ~he ~raporization of the-solvent and its condensation and precip~tation on the pulverized cinnamaldehyde-bearing material, (e.g. ~ c~nn~ -n bark~ -basic catalyst mixture (e.g., Mg(OH)2 is cor.tinuous so that the extracting operation may be carried on as long as may be necessary in order to remove the reaction product, that is, the high benzaldehyde and acetaldehyde-containing reaction product from the pulverized cinnA~aldehyde-bearing materlal~ (e.a., cinna~non bark) to the extent desired. Ordinarily, the vaporization and condensation of the solvent will not keep pace with its discharge through the siphon 90 that the operation of the apparatus so far as withdrawal of the solvent and extraction is concerned, will be intermittent. That is, a certain amount of the solvent will collect and remain in contact for a time with ,the pulverized cinna -ldehyde-bearing material (e.g., pulverized cinnA ,n bark or pulverized cinn;~ n leaf) and then will be discharged, the holder being practically emptied of liquid before the siphoning action is stopped.

* * * * *

Figure 7A is a schematic diagram of a liquid-liquid phase reaction-product recovery apparatus which can be used to carry out the retro-aldol reaction of our invention, to wit:

, . , ~ tE~ E]>

;j ~ ~
, Set forth in Figure 7A is a liquid-liquid retro-aldol reaction-product recovery apparatus which is composed of a reaction vessel 169 attached to a packed refluxing column 181 containing packing (e.g., Raschig Rings or Berle Saddles) 182 up to level 183, which, in turn, is connected to the condenser/vapor line/product recovery-return system (hereinafter referred to as the "CVPRR system. The "CYPR" system consists of vapor line 185 containing the-~ eter or temperature gauge 186 connected back into the main column through llne 188~ at the very top of the column is condenser 199 surrounded by cooling liquid in ~acket 202 with the cooling liquid entering at 201 and exiting at 203. Fixed ~unnel 187 is located below condenser 199 which has opening 200 leading into fixed funnel 187. Liquid from fixed funnel 187 is directed into movable funnel 189 which is caused to be moved by means of magnet 193 operated using magnetic coil 191 using electric timer 192. Movable funnel 189 can cause llquid to be directed back onto packing surface 183 through space 184 or the liquid may be directed into tube 194 through opening 190. Hence, according to the way the electric timer is set~ condensed liquid may intermittently be directed back into the packing or into recovery tube 194 past valve 197 through tube 205 past valve 207 through tube 216 and opening 217 into separatory funnel 218. Material having a higher vapor pressure such as acetald~hyde proceeds through tube 206 past valve 208 passed ~T~ joint 211 through valve 210 and tube 226 through opening 227 into cold trap 231 wherein the substantially pure acetaldehvde containing minor impurities is collected (shown by reference numeral 230).

f ~

. . .
In carrying the reaction:

~ ' O
~ t8~']~

a liquid-bearing cinnamaldehyde substance, e.g., cassia oil or cinni -n oil or natural solvent-containing cassia oil or cinnamon oil l is placed in reaction vessel 169. Simultaneously, or subsequently base, e.g., sodium carbonate or sodium bicarbonate or proline or choline is placed in reaction vessel 169 with stirring by stirrer 173 powered by stirrer motor 175 through shaft 174. Simultaneously, a nitrogen blanket is maintained over the stirred reaction mass using nitroqen gas pumped in through opening 176 into the reaction vessel 169 at orifice 177.
Reaction mass 170 may also contain water or a Cl-C5 lower alkanol such as ethyl alcohol or a mixture of water and a Cl-C5 lower alkanol. Heating mantle 171 containing heating elements 172 is energized while the stirrer motor is in operation causing the reaction mixture 170 to undergo a reaction whereby a mixture of ci~n~ ~ldehyde, acetaldehyde and benzaldehyde together with either of the Cl-C5 alkanol solvent or the Cl-C5 alkanols solvent/water mixture or water is vaporized through opening 180, and reaction flask neck 179 into packed column 181 containing packing 182 and having a packinq surface at 183. The vapor is partially condensed in the packing 182 and the condensed material returns through the packing back into the reaction flask for subse~uent reaction.

Simultaneously, part of the vapor proceeds through vapor tube 185 passed thermometer or temperature gauge 186 through tube 188 back into the column and onto condenser 199. With valve 197 open with respect to tube 198, highly volatile mixture containing acetaldehyde proceeds passed the condenser 199 throu~h tube 198 passed tube 205 throuqh tube 206 (with valves 208 and 210 "open") through tube 209 and through tube 226 into cold trap 231 through opening 227. Thus, substantially pure acetaldehyde is collected at 230 using dry ice trap 228 containing dry ice at location 229.
Less volatile condensate (e.g., a mixture rich in cinnA~ldehyde and benzaldehyde and containing smaller amounts of acetaldehyde is condensed at 199 and the condensate passes back through opening 200 into fixed funnel 187. The condensate then proceeds into movable funnel 189 wherein part of the condensate is returned through space 184 into packing 182 and then back into the reactor 169 for subse~uent reaction and part of the condensate is directed into tube 194 through opening 190 intermittently as a result of the setting of electric timer 192 which operates magnetic coil 191 which actuates magnet 193 causing movable funnel 189 to move laterally; at one point in the ti~.e interval causing fluid to enter opening 190 and at another point in the time interval causing fluid to enter the packed column 181 through packinq 182. Hence with valve 197 open with respect to tube 194-196, benzaldehyde/cinnamaldehyde reaction product passes through the HU~ tube 195 past valve 197 through tube 205 past valve 207 (in open position) through tube -216 through opening 217 into separatory funnel- 218 wherein water or mixture of water and alkanol or alkanol separates out~ The benzal-dehydefci~ ldehyde mixture is located at location 220 and thewater or water~alkanol mixture of alkanol is at location 219 separated at phase separation location 221. When the separatory funnel fills, valve 222 is opened permittin~ benzaldehyde/cinna-maldehyde mixture 200 to proceed into product container 224 at location 225.

~1 1 3 3 6 1 2 7 When valve 207 is open, simultaneouslv acetaldehyde vaPors not condensin~ may still pass through tube 206 with valve 208 and valve 210 open and valve 212 and 213 closed with the acetaldehyde condensing in cold trap 231 coo~ed by dry ice 229 in container 228 otherwise vapors are vented to the atmosphere if valve 210 is closed and va~ves 208, 212 and 213 are open with 'the acetaldehyde passing through tube 206 and past tube 214.
In addition, other vapors may pass through tube 215 through tube 213 into the open atmosphere.

Referring to Figure 7B, Figure 7B shows magnetic coil 191 in the vicinity of magnet 193 whereby movable funnel 189 may be moved so that the funnel may be positioned to direct liauid coming into same from funnel 187 either into tube 190 for recovery purposes or back onto packed column 181 (on packina 182) for recycle purposes.

Referring to Figure 7C, Fia,ure 7C is a "continuous apparatus"
version of the batch type apparatus of Figure 7A.

In actuality, Figure 7C is a schematic diagram of a continuous liquid-liquid phase reaction-product recovery apparatus which can be used to carry out the retro-aldol reaction of our invention, to wit:

~ '] ~ 1 Set forth in Figure 7C is a liquid-liquid retro-aldol reaction-product recovery apparatus which is composed of a reaction vessel 304 attached to a packed refluxing column 305 -~ ~
containing packing 306 which, in turn, is connected to a cooling heat exchanger 321 containing heat exchange tubes 322 cooled using cooling liquid entering at 323 and exitina at 324, which, in turn, is connected to product recovery and recycle system composed of lines 325, 327,two-way valve 326, line 328, valve 329,.
pump 330 and line 331 and receiver 332.

In carrying out the reaction:

~o O
~ ~ >~/+~h ~ J

.. i a liquid-bearing cinnA~Aldehyde substance, e.~., cassia oil or C~ nn- -n oil or natural solvent-containing cassia oil or ci n~ _r oil 310 contained in container 309 is pumped through line 313 past valve 314 using pump 315 through line 316 into reactor 304. Simultaneously, or subsequently, base 312 such as aqueous sodium bicarbonate contained in holding tank 311 is pumped through line 317 past valve 318 using pump 319 throuqh line 320 into reactor 304 at location 300. The resulting mixture 300 which may also contain a Cl-C5 lower alkanol such as ethyl alcohol and/or water is heated to reflux and refluxed in packed column 305 having packing 306 (e.~., Raschig Rings or Berle Saddles) while being stirred by stirrer 303. The refluxing substance is continued to be refluxed in packed column 305 having packing 306 until analysis indicates that a desired ;amount of benzaldehyde and acetaldehyde has been formed in the reaction mass 300 whereupon the heat input into reactor 304 is increased whereby a significant portion of the reacting material is distilled overhead through heat exchanger 321 cooled using cooling liauid entering at 323 and exiting at 324. The resultin,q ;condensed material is passed through line 325 passed reflux valve 326 through line 328 past valve 329 using pump 330 through line 331 into receiving vessel 332. A portion of the condensed material may be refluxed back into the reactor 304 past reflux valve 326 through line 327 through pipe 308 back into the packed column 305 containing packing 306 and then back into the reactor 304. In receiver 332, the lower phase is benzaldehyde and acetaldehyde-rich (indicated by reference numeral 334) and the uppér phase is solvent-rich (e.q., water and/or lower alkanol), reference numeral 333. The benza _ehyde and acetaldehyde-rich phase is then pumped into opening 338 through line 335 using pump 336 past valve 337 through line 339 into distillation column 340 at location 341 where overhead acetaldehyde-rich material is distilled through line 342 past reflux valve 343 through line 345 past valve 346 using pump 347 through line 348 into receiver 350, the acetaldehyde-rich material being indicated by reference numeral 349. The bottoms which are benzaldehyde and cinn~ ildehyde-rich are removed through line 351 past return valve 352 through line 354 past valve 355 using pump 356 through line 357 into receiver 358 with the benzaldehyde/cinnamaldehyde-rich phase indicated by reference numeral 3S9. With regard to distillation column 340, line 344 is the reflux line for the acetaldehyde-rich phase and line 353 is the reboiler line for the benzaldehyde/cinn; aldehyde-rich phase.

- The benzaldehyde/cinnamaldehyde-rich phase 359 may then be redistilled in distillation column 365 by passing the contents of receiver 358 through line 360 past valve 361 using pum~ 362 passed line 363 into distillation column 365 at location 364.
Overhead distillate rich in benzaldehyde is then removed throuah line 366 past reflux valve 367 through line 370 past valve 368 using pump 369 into receiver 371, the benzaldehyde-rich material being indicated by reference numeral 37~. The bottoms which are cinni i~ldehyde-rich are removed through line 373 past return valve 3,4 through line 378 using pump 377 past valve 376 into receiver 379, the cinn~ ehyde-rich phase indicated by reference numeral 380. The bottoms return line is indicated by reference numeral 375.

The aforementioned batch apparatus is used in the practice of Example VIt infra.

j Figure 8 is the GLC profile for the reaction product of Example VI wherein the reaction: !
+~o H ~

takes place. The peak indicated by reference numeral 800 is the peak for benzaldehyde. The peak indicated by reference numeral 810 is the peak for the cinnamaldehyde.

Figure 9 is the GLC profile for a first distillation product of the reaction product of Example VI rich in benzaldehyde. The peak indicated by reference numeral 900 is the peak for benzaldehyde.

Figure 10 is the GLC profile of a second distillation product of the reaction product of Example VI rich in benzaldehyde. The peak indicated by reference numeral 101 is the peak for benzaldehyde.

Figure 11 is the GLC profile of a third distillation product of the reaction product of Example VI rich in benzaldehyde. The peak indicated by reference numeral 111 is the pea~ for the benzaldehyde.

-52- ~

Figure 12 is the total ion current spectrum of a GC-MS
analysis of the acetaldehyde-rich material condensed in the ~cold trap" 231 as indicated by reference numeral 230 on Figure 7A.
The peak indicated by reference numeral 120 is the peak for acetaldehyde. The shoulder indicated by reference numeral 121 is for ethyl alcohol. The peik indicated by reference numeral 122 is the peak for acetic acid. The peak indicated by reference numeral 123 is the peak for crotonaldehyde. The peak indicated by reference numeral 124 is the peak for benzaldehyde.
.
In further illustration of this invention the following examples are given. The instant invention should not be - ,limited to these examples but is only limited by the scope of the claims as set forth, infra.

EXAMPLE I

PREPARATION OF NATURAL BENZALDEHYDE-CINNAMALDEHYDE MIXTURE

Reaction:

~0 ~OH

~ H;~,o ~

~ J ~ 3 Into a 250 ml, three neck flask is placed 10 grams cassia oil, 50 ml ethanol (95% foodgrade), 50 ml distilled water and 2 grams of L-proline (natural). Boiling chips are added and a water-washed stream of nitrogen is past over the reaction mass to help prevent oxidation of the formed benzaldehyde. The mixture is heated to reflux and refluxed for a period of 18 hours at atmospheric pressure (82C).

The resulting product contains 40% benzaldehyde and 60 cinnamaldehyde.

I Figure 1 is the GC-IR spectrum for the resulting product.
The peak indicated by reference numeral 10 is the peak for the benzaldehyde reaction product. The peak indicated by reference I numeral 11 is the peak for the unreacted cinnamaldehyde.
I!
The resulting material is fractionally distilled. The 'bottoms at the end of the fractional distillation are analyzed.

Figure 2 is the GC-IR spectrum for the bottoms in the distillation pot. The peak indicated by reference numeral 20 is the peak for benzaldehyde. The peak indicated by reference numeral 21 is the peak for the cinnamaldehyde.

EXAMPLE II

PREPARATION OF
NATURAL CINNAMALDEHYDE AND NATURAL BENZALDEHYDE

Reaction: ~

Aqueous Sodium Carbonat~

~ + ~C~
J

Into a three neck flask equipped with stirrer, thermometer and reflux condenser is placed 10 grams of cassia oil and 100 ml of a 3% aqueous sodium carbonate solution. Boiling chips are added and a water-washed stream of nitrosen is passed over the reaction mass to help prevent oxidation of the formed benzaldehyde. The mixture is heated to reflux and refluxed for a period of 7 hours (100C). The resulting macerial contains 70% benzaldehyde and 30% cinnamaldehyde.

Figure 3 is the GC-IR spectrum for the crude reaction mass. The peak indicated by reference numeral 3,0 is the peak for benzaldehyde. The peak indicated by reference numeral 31 is the peak for the cinnamaldehyde. (Conditions: Carbowax column programmed at 75-225C at 3C per minute).

!;

,i l I ~ 1 EXAMPLE III
' At the rate of 3% to two separate samples of natural cherry liquer the product of Example I and the product of Example II
are added. In each of the cases the resulting cherry liqueur has a more natural, more aesthetically pleasing rich, ripe cherry aroma and taste nuance remeniscent of natural cherry flavor. A bench panel of five members not associated with the inventive entity of the instant application unanimously prefers the cherry liquer containing the products of Examples I and II
to the products not containing such materials.

EXA~IPLE IV

Each of the cherry liqueurs produced,L~ Example III is in-timately admixed with carbonated Perrier ~ water at the weight ratio of 50:50 (Perrier ~ water;cherry liquer), The resulting "carbonated" beverage haQ an excellent, natural cherry aroma and taste. A bench panel of five members prefers the "resulting cherry soda" to a similar cherry soda produced without the use of the products of Examples I or II.

EXAMPLE V

A cherry fruit puree is produced (for the purpose of adding to an unflavored yogurt). At the level of 0.1%, each of the products of Examples I and II i8 added to separate samples of the cherry puree. At the rate of 10% each of the cherry puree samples is added to unflavored yogurt and intimately admixed therewith. A bench panel of five members not associated with the inventive entity of the instant application unanimously prefers the cherry flavored yogurt containing the products of ~Examples I and II to the same product not containing such materials.

! -57-; EXAMPLE VI

PREPARATION OF
NATURAL BENZALDEHYDE-CINNAMALDEHYDE MrxTuRE
AND NATURAL ACETALDEHYDE C~MPOSITION

Reaction: .
~i ~0 ~ O
Ho > [~+lh Into a reaction vessel in the apparatus as set forth in Figure 7A, equipped with stirrer, thermometer and reflux packed column fitted with overhead condenser to which are connected receivers for benzaldehyde-rich materials and acetaldehyde-rich materials as ~pecified, supra, are placed 1 liter of water, 50 grams cassia oil and 20 ml of a 45% solution of choline base in methyl alcohol.

The reaction mass is heated to reflux and maintained at reflux for a period of 0.5 hours, at which point in time, 20 ml of a 45% solution of choline base in methanol is added.
The reaction mass is continued to be refluxed for a period of 4 hours, slowly removing the methanol from the system through the overhead condenser with the reflux temperature rising from 65 to 99C. At the end of the 4 hour period, 300 ml water is added to the reaction mass. The reaction mass is then refluxed for a period of 8 hours. At the end of the 8 hour refluxing period, additional heat is imparted to the reaction vessel whereby the reaction product begins to be distilled usin~ the overhead ~ - ~c~

condenser 199 and the controlled reaction product recovery apparatus shown in Figures 7A and 7B into (i) receiver 218 where the benzaldehyde-rich fraction 220 is collected and tii) cold tràp 231 where the acetaldehyde-rich material 230 is condensed and collected.

¦ The original cassia oil utilized contained 88% cinnamal-dehyde.
The yield of benzaldehyde based on 88% cinnamaldehyde-con-taining cassia oil iR 65%. The third distillation fraction contained a ratio of benzaldehyde:cinnamaldehyde of 13:1.

Figure 8 is the GLC profile of the reaction product prior to the first distillation. The peak indicated by reference numeral 800 is the peak for benzaldehyde. The peak indicated by reference numeral 810 is the peak for cinnamaldehyde.

Figure 9 i8 the GLC profile for the first distillation of the benzaldehyde-rich phase 89. The peak indicated by reference numeral 900 is the peak for ben~aldehyde.

Figure 10 iq the GLC profile for the second distillation of the lower phase benzaldehyde-rich product. The peak indicated by reference numeral 101 is the peak for benzaldehyde.
v Figure 11 is the GLC profile for the third distillation of the benzaldehyde-rich phase. The peak indicated by reference numeral 111 is the peak for benzaldehyde.

Figure 12 is the total ion current spectrum of a GC-~S
analysis of the acetaldehyde-rich composition containing minor impurities 230 trapped in cold trap 231 of the aPparatus of Figure 7A. The peak indicated by reference numeral 120 is the peak for the acetaldehyde. The shoulder indicated by reference numeral 121 is for ethyl alcohol. The peak indicated by ;reference numeral 122 is the peak for acetic acid. The peak indicated by reference numeral 123 is the peak for croton-aldehyde. The peak indicated by reference numeral 124 is the peak for benzaldehyde, EXAMPLE VII

The following sweet cherry flavor formulation is prepared:

Ingredients Parts by Weight Allyl isovalerate..,...,,,,,~,,,,,, lS.0 Amyl butyrate.... ..,,..-,,,.,,,~, 200.0 Anisic aldehyde.. ,,.,.......,......... 37.0 Anisyl acetate~.,,.,,,,~,,..,,,, 25.0 Anisyl butyrate..............,........ 12.0 Anisyl propionate.. ~.~,..... .,........ 12.0 Benzyl acetate..... ,..,..... ..,.~..... 50.0 Third distillation product of the reaction product of Example VI ~identified ..... ,,.4~658.0 by the GLC profile of Figure II) Eugenol~.. ~...... ~....,.. .,... ,,,.... 7.0 Cyclohexyl cinnamate..,......... 5.0 Cyclohexyl formate...,.,.,,,,,,.,,, 8.0 Ethyl acetate,...........,,,.. ,.. , 680.0 Ethyl butyrate....,.,,,,,,,,.,...... 152.0 Ethyl methylglycidate~....,,..,..., 100.0 Rhodinol,,,,,,,~.. ~,,,,,,,. 60.0 Beta-ionone.~,~... ,,.... ,.. ,,,,., 4.0 Jasmine absolute,,,,,,,,,.,,,,.,,,, 13.0 Citral.. ,,,.,.,..,,,,,,,,,,,,...... 1.0 Maltol (5% in ethanol)..,,,,,.. , 1.0 Orris butter.......... ,...... ,,.,.,,.... 30.0 Orris resinoid.................. 160.0 Rhodinyl formate...... ,,,.,.. .,......... 1.0 Rhodinyl isovalerate......... ..,........ 12.0 Para-Toluic aldehyde.. ~.. , 500-0 Vanillin ..~................... 400.0 Propylene glycoL .,,..,.~ ,,, 2,920.0 , .
- Total 10,000.0 The resulting flavor is compared with the same flavor produced usi~g a mixture of bitter almond essential oil and extracted Ceylon cinn c~ cinna~aldehyde in a combined amount of 4658.0 parts by weight (grams). The cherry flavor containinq the third distillation product of the reaction product of Example VI is unanimously preferred b~ a bench panel of five members independent of the inventive entity of the instant patent application due to the more natural nature of the overall flavor.
The natural cherry nuances imparted using the third distillation product of the reaction product of Example VI give rise to un-expected, unobvious and advantageous properties of the resulting cherry flavor formulation.
~' .

, I
i !
!!

i EXAMPLE VIII

A. Powder ~lavor Formulation Twenty grams of the flavor composition of Example VII is emulsified in a ~olution containing 300 grams gum acacia and 700 grams of water. the emulsion i8 spray dried with a Bowen Lab Model Drier utilizing 260 c.f.m. of air with an inlet temperature of 500F and an outlet temperature of 200F and a wheel speed of 50,000 rpm.

B. Sustained Release Flavor The fol~lowing mixture is prepared:
Ingredients Parts by Weight Liquid cherry flavor .,............... 20 composition of Example VII
Propylene glycoL...................... 9 Cab-O-Sil(~) M-5 (brand of silica produced , .
by the Cabot Corp. o f ............ 5 125 High Street, Boston, ~ss. 02110) Physical properties:
Surface area:............ 200 m2/gm Nominal particle size:... 0.012 microns Density:................. 2.3 lbs/cu.ft.

The Cab-O-Sil~ is dispersed in the liquid cherry flavor composition of Example VII with vigorous stirring thereby resulting in a viscous liquid. Seventy-one parts by weight of the powder flavor composition of Part A, supra, is then blended into said viscous liquid with stirring at 25C for a period of 30 minutes resl~ltinq in a dry, free-flowing sustained release flavor powder.

*Trade Mark EXAMPL~ IX

Ten parts by weight of 50 Bloom pigskin gelatin is added to ninety parts by weisht of water at a temperature of 150F. The mixture is agitated until the gelatin is completely dissolved and the solution is cooled to 120F. Twenty parts by weight of the liquid flavor composition of Example VII is added to the colution which is then homogenized to form an emulsion having a particle size typically in the range of 5-40 microns. The material is kept at 120F under which conditions the gelatin will not gel.

Coacervation is induced by adding slowly and uniformly, forty parts by weight of a 20% aqueous solution of sodium sulphate. During coacervation of gelatin, molecuLes are deposited uniformly about each oil droplet as a nucleus.

Gelation is effected by pouring the heated coacervate mixture into 1,000 parts by weight of a 7% aqueous solution of sodium sulphate at 65F. The resulting gelled coacervate may be filtered and washed with water at temperatures below the melting point of gelation, to remove the salt.

Hardening of the filter cake, in this example, is effected by washing with 200 parts by weight of 37% solution of formaldehyde in water. The cake is then washed to remove the residual formaldehyde.

j !
EXAMPLE X

CHEWING GUM

One hundred parts by weight of chicle are mixed with four parts by weight of the flavor prepared in accordance with Example VIII, Part B. Three hundred parts of sucrose and one hundred parts of corn syrup are added. Mixing i8 effected in a ribbon blender with jacketed side walls of the type manufactured by the Baker Perkins Co.

The resultant chewing gum blend is then manufactured into strips one inch in width and O.l inches in thickness. The strips are cut into lengths of three inches each. On chewing, the chewing gum has a pleasant, long-lasting natural cherry flavor.

EXAMPLE XI

One hundred parts by weight of chicle are mixed with eighteen parts by weight of the flavor prepared in accordance with ~xample IX. Three hundred parts of sucrose and one hundred parts of corn syrup are then added. Mixing is~effected in a ribbon blender with jacketed side walls of the type manufactured by the Baker Perkins Co.

The resultant chewing gum blend is then manufactured into strips one inch in width and 0.1 inches in thickness. The strips are cut into lengths of 3" each. On chewing, the chewing gum has a pleasant, long-lasting natural cherry flavor.

~XAMPLE XII

TOOTHPASTE FORMULATION

.
i~ The following separate groups of ingredients are prepared:

Parts by Weight Ingredients Group "A"
30.200...................... Glycerine 15.325...................... Distilled water 0.100...................... Sodium benzoate 0.125...................... Saccharin sodium 0.400...................... Stannous fluoride Group "B"
12.500...................... Calcium carbonate 37.200...................... Dicalcium phosphate (dihydrate) Group "C"
2.000...................... Sodium n-lauroyl sarcosinate (foaming agent) Group "D"
1.200...................... Flavor material of Example VIII, Part B
100.000...................... (Total) Procedure:
1. The ingredients in Group "A" are stirred and heated in a steam jacketed kettle to 160F.
2. Stirring is continued for an additional three to five minutes to for~ a homogeneous gel.
~3. The powders of Group "B" are added to the gel, while mixing until a homogeneous paste is formed.
'4. With stirring, the flavor of "D" is added and lastly, the sodiu~ n-lauroyl sarcosinate.
! 5. The resultant slurry is then blended for one hour. The completed paste is then transferred to a three roller mill and then homogenized, and finally tubed.
The resulting toothpaste, when used in a normal toothbrushing procedure, yields a pleasant, sweet, cherry flavor of constant strons intensity throughout said procedure (1-1.5 minuteJ).

- ` .

EXAMPLE XIII

CHEWABLE VITAMIN TABLETS

The flavor material produced according to the process of Example VIII, Part B, is added to a chewable vitamin tablet formulation at a rate of 10 gm/kg which chewable vitamin tablet formulation is prepared as f~ollows:

In a Hobart Mixer, the following materials are blended to homogeneity:
Ingredients Gms/1000 Tablets Vitamin C (ascorbic acid as ascorbic acid-sodium ascorbate mixture 1~ ........... 70.000 Vitamin Bl (thiamine mononitrate) as Rocoat ~
thiamine mononitrate 33-1/3%
(Hoffman LaRoche) ....................... 4.000 ¦Vit~mi ~2 (riboflavin) as ¦Rocoat ~ riboflavin 33-1/3%¦............ 5.000 Vitamin B6 (pyridoxine hydrochloride) as Rocoat pyridoxine hydrochloride 33-1/3% .........4.000 ¦Niacinamdie as Rocoat ~ ¦
niacinamide 33-1/3% ¦....... ~.......... 33.000 Calcium pantothenate................... 11.000 ¦Vitamin ~12 (cyanocobalami~¦
! las Merck 0.1% in qelatin ............. 3.500 Vitamin E (dl-alpha topcopheryl acetate) as dry Vitamin E
acetate 33-1/3% Roche ................. 6.600 d-Biotin............................... 0.044 Certified lake color................... 5.000 ¦ Flavor of Example VIII, Part B......... as indicated above Sweetener sodium saccharin............. 1.000 Magnesium stearate lubricant........... 10.000 Mannitol q.s. to make.................. 500.000 *Trade Marks Preliminary tablets are prepared by slugging with flatfaced punches and grinding the slugs to 14 mesh. 13.5 Grams dry Vitamin A acetate and 0.6 grams Vitamin D are then added as beadlets. The, entire blend i8 then compressed using concave ! punches at 0.5 grams each.
I
Chewing of the resultant tablets yields a pleasant, long-lasting, consistently strong,.cherry flavor for a period of 12 minutes.

t 3361 27 EXAMPLE XIV

CHEWING TOBACCO

Onto 100 pounds of tobacco for chewing (85% Wisconsin lead and 15% Pennsylvania lead) the following casing is sprayed at a rate of 30%:

Ingredients Parts by Weight Corn syrup.......................,~ 60.0 Licorice........................ ,.~ 10.0 Glycerine............................... 20.0 Fig juice...................... ,.,,, 4.6 ~ Prune juice............................. 5.0 - ~lavor material of Example ~III of Part B ~ ,. .................... ~,. 0~4 The resultant product is redried to a moisture content of 20%. On chewing, this tobacco has an excellent substantially consistent, long-lasting, sweet, cherry nuance (20 minutes) in conjunction with the main fruity tobacco note, ~ l i B AMPLE XV
! ` ` F~AVOR~D FOODSTUFF

2.25 Ounces of a coconut macaroon mix distributed by Drake Bakeries, Division of Borden,~Inc. of Columbus, Ohio 43215 is intimately admixed at the le~e of 20 ppm with the benzaldehyde/cin-namaldehyde mixture (second distlllation product) prepared according to Example VI.
"
The coconut macaroon composition contains corn syrup, coconut, sugar and egg white.
,; .
The coconut macaroon composition is then baked at 325F at atmospheric pressure for a period of 20 minutes. The resultant coconut macaroon cookies have an excellent ~natural coconut~
notes with intense almond nuances not present in the cookies without the composition of Example ~I.

When the composition of Example VI is replaced with the compositions of Examples I or Ii, a similar'hatural coconut"
~l sr' nuance is created.

l -69- 1 3~6 1 27 , I .
EXAMPLE XVI

TOBACCO FLAVOR FORMULATION AND TOBACCO

A tobacco mixture is produced by admixing the following materials:

Ingredients ~ Part~ by Weight Bright............................. ~ 40.1 Burley............................. ,,,, 24.9 Maryland........................... ,,,, 1.1 Turkish......................... ,.. ..,, 11.6 Stem ~flue-cured)................ ,,,,, 14.2 Glycerine.......................... ,,,, 2.8 Water................................... 5~3 Cigarettes having cellulose acetate filters are prepared from this tobacco:

The following flavor formulation is prepared:

; Ingredient~ Parts by Weight Ethyl butyrate.................... ,.~., .05 Ethyl valerate.................. ~..... .05 " Maltol.......................... ,.... 2.00 Cocoa extract....................... 26.00 ! 'Coffee extract.................... ,,. 10.00 Ethyl alcohol (95% aqueous)........... 20.00 Water................................. 41.90 The above-stated tobacco flavor formulation is applied at the rate of 0.1% to all of the cigarettes produced using the above tobacco formulaton. One-third of the cigarettes are then treated in the tobacco section thereof with 5 ppm of the benzaldehyde/ci~n~r-ldehyde mixture produced by the third distillation of Example VI. One-third of the cigarettes are treated onthe cellulose acetate filter with 1 microliter of a 0.1~ ethanol solution of the cinnamaldehyde/benzaldehyde mixture of the third distillation of Example VI.

i , ! 70 Il The above-stated tobacco formulation is applied at the rate of 0.1 % to all of the cigarettes produced using the above tobacco formulation. One-third of the cigarettes are then , treated in the tobacco section thereof with 5 ppm of benzal-dehyde/ci~n~r~ldehyde mixture produced by the third distil-lation of Example VI. One-third of the cigarettes are treated on the cellulose acetate filter with 1 microliter of a 0.1%
ethanol solution of the cinnamaldehyde/benzaldehyde mixture of the third-distillation of Example VI.
', , The control cigarettes not containing the mixture of ben-zaldehyde and cinnamaldehyde produced according to the process of Example VI and the experimental cigarettes which do contain the mixture of benzaldehyde and cinnamaldehyde produced accord-ing to the process of Example VI are evaluated by three-way comparison, and the results are as follows:
In aroma, the cigarettes containing the benzaldehyde and cinnamaldehyde of Example VI in the tobacco or in the filter have been found to be sweeter and fruitier with faint aesthetically pleasing cherry nuances.

In ~moke flavor, the cigarettes containing the benzaldehyde and cinnA aldehyde mixture are more aromatic, more sweet, ;j,fruitier and slightly less harsh in the mouth and throat. In addition, those cigarettes containing the benzaldehyde and cinnamaldehyde mixture of Example VI in the tobacco give rise to a fruity nuance in the taste and aroma on smoking.

~ o l ~

EXAMPLE XVII

! APPLE FLAVOR FORMULATION

The following basic apple flavor formulation is prepared:

; Ingredients . Parts by Weight Amyl acetate............................ 1.0 Gamma decalactone.................................... 1.5 Caproic acid.......... ~.............................. 1.5 n-Hexyl acetate........... ........................... 2.5 Coriander Oil............. ........................... o,5 n-Hexyl iso-butyrate...... ........................... 2.5 n-Hexanal................. ........................... 5.0 Ethyl isovalerate......... ........................... 5.0 cis-3-~eYer~ol .. - ... - .................. - - .. - .. - 18.0 Ethyl-2-methvl butyrate............. 18.0 trans-2- ~eYe~A ~ 18.0 Apple Fusel Oil..................... 26.0 ~altol.............................. 0.5 95% food grade ethanol~...,........ 100.0 :~ .
.

This basic apple flavor is compared, in water, with and without the addition of natural acetaldehyde prepared according to Example VI at the rate of 6 ppm and at the rate of 10 ppm in water. The flavor with the addition of the natural acetaldehyde composition has a fresh apple ~uice character with light fruity ! -72-i topnotes. Both notes are missin~ in the flaYor that does not contain the natural acetaldehyde composition of Example ~I~ For ,this reason, the flavor with the natural acetaldehyde composition of Example VI is preferred unanimously by a three-member bench panel.

1 33~ 1 ~ 7 _.
EXAMPLE XV I I I

A. POWDER FLA~OR ~ORMULATION

20 Grams of the flavor formulation of Example IV is emulsi-fied in a solution containing 300 g ~um acacia and 700 g water, The emulsion is spray-dried with a Bowen Lab Model Drter utilizing 260 c.f.m. of air with an inlet temperature of 500F., an outlet temperature of 200F and a wheel speed of 50,000 rpm.

B. SUSTAINED RELEASE FLAVOR

; The following mixture is prepared:

Ingredients Parts by Weight ~iquid Apple Flavor of ;
Example rv 1.................... 20.00 Propylene Glycol.................. 9.00 Cab-O-Sil~-5 ~rand of Silica produced by the Cabot Corporation of ... 5.00 125 High Street, Boston, Mass. 02110:

(Physical Properties:
Surface Area:...--.-------- 200 m2/qm ~ Nominal particle size:----- 0.012 microns ! Density:........ -.-------- 2.3 lbs/cu.ft.) , ~ ., ~he Cab-O-Sil is dispersed in the liquid apple flavor composition of Example XVII with vigorous stirrinq, thereby resulting in a iscous liquid. 71 Parts by weight of the powder flavor composition of Part 1, suPra, is then blended into the said viscous liquid, with stirring at 25C for a period of 30 minutes, resulting in a dry, free flowin-g sustained release powder.

1~36127' BAMPLE ~:rX
,;
10 parts by weight of 50 Bloom pigskin gelatin ifi added to 90 parts by weight of water at a temperature of 150F. The mixture is agitated until the gelatin is completely dissolved and the solution is cooled to 120F. 20 parts by weight of the liquid apple flavor composition of ExampleXVII is added to the solution which is then homogenized to form an emulsion having particle size typically in the range of 5-40 microns. This material is kept at 120F under which conditions, the gelatin will not jell.

Coacervation is induced by adding slowly and uniformly, 40 parts by weight of a 20% aqueous solution of sodium sulphate.
During coacervation the gelatin molecules are deposited uni-formly about each oil droplet as a nucleus.

Gelation is effected by pouring the heated coacervate mixture into 1,000 parts by weight of 7% aqueous solution of sodium sulphate at 65F. The resulting jelled coacervate may be filtered and washed with water at temperatures below the melting point of gelatin, to remove the salt.

r Hardening of the filtered cake, in this example, is effected by washing with 200 parts by weight of 37~ solution of formaldehyde in water. ~he ca~e is then washed to remove residual formal~ehyde.

1 33~
. .

EXAMPLE XX
- , CHEWING GUM

100 parts by weight of chicle are mixed with 4 parts by weight of the flavor prepared in accordance with EXampleXVIII~).
300 Parts of sucrose and 100 parts of corn syrup are added.
Mixing is effected in a ribbon blender with jacketed walls of the type manufactured by the Baker Perkins Co.

The resultant chewing gum blend is then manufactured into strips 1 inch in width and 0.1 inches in thickness.
The strips are cut into lengths of 3 inches each. On chewing, the chewing gum has a pleasant, long lasting aople flavor.

133~l27 EXAMPLE XXI

CHEWING G~

100 Parts by weight of chicle are mixed with 18 parts by weiqht of the flavor prepared in accordance with ExampleXIX.
300 Parts of sucrose and 100 parts of corn syrup are then added. Mixing is effected in a ribbon blender with jacketed walls of the type manufactured by the ~aker Perkins Co.

The resultant chewing gum blend is then manufactured into strips 1 inch in width and 0.1 inches in thickness. The strips are cut into lengths of 3 inches each. On chewing, the chewing gum has a pleasant, long lasting apple flavor.

13361~1 "
!

EXAMPLE XXII
i TOO~HPASTE FORMULATION

The following separate groups of ingredients are pre-pared:

Parts by Weight Ingredient _ _ _ _ Group ~A~
30.200 .... ,.. ,...................... ..Glycerine 15.325 .... ,......................... ..Distilled Water .100 ......... .................... ..Sodium Benzoate .125 ......... .................... ..Saccharin Sodium .400 .......... .................... ..Stannous Fluoride Group ~
12.500 .......... .................... ..Calcium Carbonate 37.200 ....... ,...................... ..Dicalcium Phosphate (Dihydrate) ~roup ~C~
2.000 .... ,......................... , Sodium N-Lauroyl Sarcosinate (foaming . agent) Group ~D~
1.200 .... ....,............ ,........ ..Flavor Material of Example XvI~I(B) 100.00 - TO~AL

1 ~3~

1, Procedure: `
. The inqredients in Group ~A" are stirred and heated in a steam jacketed kettle to 160F.
2. Stirring is continued for an additional three to five minutes to form a homogeneous gel.
3. The powders of Group "B" are added to the gel, while mixing, until a homogeneous paste is formed.
4. With stirring, the flavor of "D" is added and lastly the sodium-n-lauroyl sarcosinate.

5. The resultant slurry is then blended for one hour.
The completed paste is then transferred to a three roller mill and then homogenized, and finally tubes.

The resulting toothpaste, when used in a normal tooth-brushing procedure yields a pleasant apple flavor, of constant strong intensity throughout said procedure (1-1.5 minutes).

133612~

EX~PLE XXIII
CHE~'ABLE VIm~IN TABLE~S

The flavor materi~ produced according to the process of Example XVIII(B) is added to a Chewable Vitamin Tablet Formulation at a rate of 10 gm/Kg, which Chewable Vitamin Tablet Formulation is prepared as follows:

In a Hobart Mixer, the followin~ materials are blended to homogeneity:

Ingredients Gms/1000 Tablets Vitamin C (ascorbid acid) as ascorbic acid-sodium ascorbate mixture 1:1 ..................... 70.11 Vitamin Bl ~thiamine mononitrate) as Rocoat thiamine mononitrate 33 1/3~ (Hoffman La Roche) ................. 4.0 jVitamin ~ (rl~oslavln) as ¦ Rocoat ~ riboflavin 33 1/3~¦.............. 5.0 vltamin ~6 ~pyrlaoxlne nydroc~lorlde)' as Rocoat ~ pyridoxine hvdrochloride 33 1/3% ~. 4.0 ¦Niacinamide as Rocoat ~ niacinamide¦
33 1/3~ 1.... 33.0 Calcium pantothenate......................... 11.5 ¦Vitamin 812 (cya~ocob~lamin) asl ~Merck 0.1~ in gelatin ¦..................... 3.5 IVitamin E (dl-alpha to~opheryl acetate)l ¦ as dry Vitamin E acetate 33 1/3~ ¦ 6.6 d-Biotin.................................... 0.044 Flavor of Example ~VIII(~)........... (as indicated abovei Certified lake color......................... 5.0 Sweetener - sodium saccharin................. 1.0 Magnesium stearate lubricant................. 10.0 Mannitol q.-. to make-------.-.............. 500.0 ~Trade Mark 13~61 27 Preliminary tablets are prepared by Slugging with flat-faced punches and grinding the slugs to 14 mesh. 13.5 g dry Vitamin A Acetate and 0.6 g Vitamin D are then added as beadlets.
The entire blend is then compressed using concave punches at 0.5 g each.

Chewing of the resultant tablets yields a pleasant, long-lasting, consistently strong apple flavor for a period of 12 minutes.

Claims (22)

1. Apparatus for carrying out the retro-aldol reaction on naturally-occurring cinnamaldehyde:

and recovering two compositions of matter separately:
(A) a first composition rich in natural acetaldehyde; and (B) a second composition consisting essentially of natural benzaldehyde and natural cinnamaldehyde, comprising:

(i) a reaction zone comprising means for contacting a natural source of cinnamaldehyde with base, operated at a temperature in the range of 40-150°C
and a pressure in the range of from 0.2 up to 10 atmospheres, for effecting the retro-aldol reaction;
(ii) a condensation means located substantially immediately upstream from the reaction zone whereat benzaldehyde and cinnamaldehyde in the vapor phase are cooled to the liquid phase for recycling or recovery;
(iii) recovery and collection means for recovery and collection of said second composition consisting essentially of benzaldehyde and cinnamaldehyde, without causing any further retro-aldo reaction on said cinnamaldehyde, said recovery and collection means being directly operable on said liquid phase whereby said second composition is recovered and collected; and (iv) recovery and collection means for collecting and condensing said first composition rich in natural acetaldehyde, immediately upstream from said condensation means whereby said first composition rich in natural acetaldehyde is recovered and collected said condensation means having a cooling capacity such that said second composition is transformed from the vapor phase into the liquid phase but said first composition is not transformed from the vapor phase into the liquid phase.

2. The apparatus of Claim 1 comprising in addition (v) a timing means for alternately (i) recycling said second composition to said reaction zone and (ii) directing said second composition to said recovery and collection means; said alternate recycling and directing being predetermined and variable depending upon the desired ultimate ratio of benzaldehyde:cinnamaldehyde in said recovered and collected second composition.

3. The apparatus of Claim 1 wherein the naturally occurring cinnamaldehyde exists in the liquid phase and intermediate said reaction zone and said condensation means is an insulated packed column.

4. The apparatus of Claim 1 wherein the naturally occurring cinnamaldehyde is in the solid phase and is in intimate contact with solid base; and said means for contacting said natural source of cinnamaldehyde with said base is such that (i) said natural source of cinnamaldehyde and base is located in a porous thimble; and (ii) water or a mixture of water and C1-C4 lower alkanol is passed through said porous thimble with a residence time such that the reaction:

is enabled to take place in the proximate location of said thimble.

5. The apparatus of Claim 1 wherein said first composition is recovered and collected in an isopropanol-dry ice-cooled trap upstream from said condensation means.

6, The apparatus of Claim 1 wherein said condensation means is a cold water condensation means operating at a temperature of between 0 and 20°C.

Claim 7: Soxhlet reaction process and recovery apparatus for (i) carrying out the retro-aldol reaction on naturally-occurring cinnamaldehyde:

and (ii) recovering two compositions of matter separately:

(A) a first recovered composition rich in natural acetaldehyde; and (B) a second recovered composition consisting essentially of natural benzaldehyde and natural cinnamaldehyde, comprising:

(i) a reaction zone means comprising means for contacting a natural source of cinnamaldehyde with base, operated at a temperature in the range of 40-150°C and a pressure in the range of from 0.2 up to 10 atmospheres, for effecting the retro-aldol reaction;

(ii) condensation and cooling heat transfer means located substantially immediately downstream from said reaction zone means, at which location benzaldehyde and cinnamaldehyde in the vapor phase are cooled and condensed to the liquid phase for recycling back to the reaction zone means or recovery and collection;

(iii) first recovery and collection means for recovery and collection of said second composition consisting essentially of benzaldehyde and cinnamaldehyde, cooled and condensed in said condensation and cooling heat transfer means, without causing any further retro-aldol reaction on said cinnamaldehyde, said first recovery and collection means being directly operable on said liquid phase whereby said second composition is recovered and collected; and (iv) second recovery and collection means for collecting and condensing said first composition rich in natural acetaldehyde located immediately downstream from said condensation and cooling heat transfer means whereby said first composition rich and natural acetaldehyde is recovered and collected, said condensation and cooling heat transfer means having a cooling capacity such that said second composition is transformed from the vapor phase into the liquid phase but said first composition is retained in the vapor phase.

Claim 8: The apparatus of Claim 7 comprising in addition (v) timing means being located as an integral part of said first recovery and collection means, and being immediately downstream from said condenser and cooling heat transfer means, for alternately (i) recycling said second composition to said reaction zone means and (ii) directing said second composition to said recovery and collection means; said alternative recycling and directing being predetermined and variable depending upon the desired ultimate mole ratio benzaldehyde:cinnamaldehyde in the recovered and collected second composition.

Claim 9: The apparatus of Claim 7 wherein the naturally occurring cinnamaldehyde exists in the liquid phase and intermediate said reaction zone means and said condensation and cooling heat transfer means is an insulated packed column.

Claim 10: The apparatus of Claim 7 wherein the naturally occurring cinnamaldehyde is in the solid phase and is in intimate contact with solid base; and said means for contacting said natural source of cinnamaldehyde with said base is constructed in a manner such that (i) said natural source of cinnamaldehyde and base are both simultaneously located in a porous thimble located in the reaction zone means; and (ii) water or a mixture of water and at least one C1-C4 lower alkanol is passed through said porous thimble with a residence time such that the reaction:

is enabled to take place in the proximate location of said thimble.

Claim 11: The apparatus of Claim 7 wherein said first composition is recovered and collected in a isopropanol-dry ice-cooled trap downstream from said first recovery and collection means.

Claim 12: The apparatus of Claim 7 wherein said condensation and cooling heat transfer means is a cold water condensation means operating at a temperature of between 0°C and 20°C.

Claim 13: Soxhlet reaction process and recovery apparatus for (i) carrying out the retro-aldol reaction on naturally-occurring cinnamaldehyde:

and (ii) recovering two compositions of matter separately:

(A) a first recovered composition rich in natural acetaldehyde; and (B) a second recovered composition consisting essentially of natural benzaldehyde and natural cinnamaldehyde, comprising:

(i) container means for housing solvent means, recovered benzaldehyde and recovered cinnamaldehyde;

(ii) means disposed beneath said container means for heating said solvent means so as to distill the same;

(iii) condenser means disposed above said container means for condensing benzaldehyde-rich and cinnamaldehyde-rich distillation vapors but not condensing acetaldehyde-rich distillation vapors;

(iv) means disposed between said container means and said condenser means for controlling the return of said condensed vapors to said container means such that the distillaton-condensation cycle proceeds automatically;

(v) said control means including means for delaying said return of said condensed vapors to said container means for a pre-determined time period during which the retro-aldol condensation reaction on cinnamaldehyde takes place;

(vi) said delay means comprising siphoning means interposed between said condensing means and said container means;

(vii) said siphoning means including adjustable means being adjustable so as to properly control said return of said benzaldehyde-cinnamaldehyde mixture to said container means in said time-delayed manner;

(viii) said siphoning means comprising a Soxhlet extractor disposed between said container means and said condenser means having said adjustable means disposed therein, said adjustable means comprising a volume displacement cylinder disposed within said extractor having dimensions approximating that of the inside wall of said Soxhlet extractor for determining the commencement of time of said siphoning of the product of the retro-aldol condensation reaction;

(ix) said retro-aldol condensation reaction taking place within said volume displacing cyclinder in the presence of a base;

(x) means disposed downstream from said condensation means for directing the acetaldehyde-rich vapors to recovery and collection means for said acetaldehyde rich vapors, said recovery and collection means for acetaldehyde vapors being separate and distinct from said container means and said condenser means.

Claim 14: The apparatus of Claim 13 comprising in addition a timing means for alternately (i) recycling benzaldehyde-rich and cinnamaldehyde-rich distillation vapors back into said siphoning means; and (ii) directing said benzaldehyde-rich and cinnamaldehyde-rich distillation vapor condensate to recovery and collection means apart from said container means; said alternative recycling and directing being predetermined and variable depending upon the desired ultimate mole ratio of benzaldehyde:cinnamaldehyde in the recovered and collected composition.

Claim 15: The apparatus of Claim 13 wherein the naturally occurring cinnamaldehyde is in the solid phase and is contained in said volume displacement cylinder; and wherein solid base is also contained in said volume displacement cyclinder and wherein the solid base is in intimate contact with the solid naturally occurring cinnamaldehyde, the residence time of the solvent means in the volume displacement cyclinder being such that the reaction:

is enabled to take place in approximate location of said volume displacement cyclinder.

Claim 16: The apparatus of Claim 13 wherein the acetaldehyde-rich composition is recovered and collected in an isopropanol-dry ice-cooled trap downstream from said condenser means.

Claim 17: The apparatus of Claim 13 wherein the condenser means is a cold water condensation means operating at a temperature of between 0 and 20°C.

Claim 18: Soxhlet reaction process and recovery apparatus for (i) carrying out a retro-aldol reaction on naturally-occurring cinnamaldehyde, said reaction being:

and (ii) recovering two compositions of matter separately:

(A) a first recovered composition consisting essentially of natural acetaldehyde; and (B) a second recovered composition consisting essentially of natural benzaldehyde and natural cinnamaldehyde, comprising:
(i) container means for housing solvent, recovered benzaldehyde, recovered acetaldehyde and recovered cinnamaldehyde;

(ii) means disposed beneath said container means for heating said solvent, said recovered benzaldehyde, said recovered acetaldehyde and said recovered cinnamaldehyde so as to distill the same thereby forming acetaldehyde vapors, benzaldehyde vapors, cinnamaldehyde vapors and solvent vapors;

(iii) condenser means disposed above said container means specifically constructed for (A) condensing benzaldehyde-rich and cinnamaldehyde-rich distillation vapors to form benzaldehyde-rich condensate and cinnamaldehyde-rich condensate but (B) not condensing acetaldehyde-rich distillation vapors;

(iv) reaction means disposed intermediate said container means and said condenser means being designed in such a manner as to be capable of fixedly housing in intimate contact said benzaldehyde-rich condensate, said cinnamaldehyde-rich condensate, said solvent and a solid base catalyst and being designed in such a way as to be capable of supporting said basic catalyst for a period of time having such a design as to enable said retro-aldol reaction to take place;

(v) control means including said reaction means disposed between said container means and said condenser means for controlling the return of said benzaldehyde-rich condensate and cinnamaldehyde-rich condensate and solvent to said container means such that the distillation-condensation cycle proceeds automatically;

(vi) said control means including means for delaying said return of said condensed vapors to said container means for a pre-determined time period during which the retro-aldol condensation reaction on cinnamaldehyde takes place;

(vii) said means for delaying comprising siphoning means interposed between said condenser means and said container means;

(viii) said siphoning means being capable of being adjusted using mass rate adjustment means so as to control the rate of return of benzaldehyde and cinnamaldehyde to said container means;

(ix) said siphoning means comprising a Soxhlet extractor disposed between said container means and said condenser means having said mass rate adjustment means disposed therein, said mass rate adjustment means comprising a volume displacement cylinder disposed within said extractor having dimensions approximating that of the inside wall of said Soxhlet extractor for determining the commencement of time of said siphoning of benzaldehyde reaction product, benzaldehyde condensate, cinnamaldehyde condensate and solvent;

(x) said retro-aldol condensation reaction taking place within said volume displacing cylinder in the presence of said solid base;

(xi) recovery and collection means capable of condensing acetaldehyde vapors into the liquid phase acetaldehyde disposed downstream from said condensation means said recovery and collections means for acetaldehyde vapors being separate and distinct from said container means and said condenser means;

(xii) means disposed downstream from said condensation means but upstream from said recovery and collection means specifically designed for directing the acetaldehyde-rich vapors to said recovery and collection means for said acetaldehyde-rich vapors.

Claim 19: The apparatus of Claim 18 comprising in addition a timing means for alternately (i) recycling benzaldehyde-rich and cinnamaldehyde-rich distillation vapors back into said siphoning means; and (ii) directing said benzaldehyde-rich and cinnamaldehyde-rich distillation vapor condensate to recovery and collection means apart from said container means; said alternative recycling and directing being predetermined and variable depending upon the desired ultimate mole ratio of benzal-dehyde:cinnamaldehyde in the recovered and collected composition.

Claim 20: The apparatus of Claim 18 wherein the naturally occurring cinnamaldehyde is in the solid phase and is contained in said volume displacement cylinder; and wherein solid base is also contained in said volume displacement cyclinder and wherein the solid base is in intimate contact with the solid naturally occurring cinnamaldehyde, the residence time of the solvent means in the volume displacement cyclinder being such that the reaction:

is enabled to take place in approximate location of said volume displacement cyclinder.

Claim 21: The apparatus of Claim 18 wherein the acetaldehyde-rich composition is recovered and collected in an isopropanol-dry ice-cooled trap downstream from said condenser means.

Claim 22: The apparatus of Claim 18 wherein the condenser means is a cold water condensation means operating at a temperature of between 0°
and 20°C.