1. OBJECTIVES 1. Types of caramel produced;
CARAMELIZATION
OBJECTIVES
1. Types of caramel produced;
2. Mechanism and major chemical reactions;
3. Caramel usage.

2. 1850г. – used for the first time in Europe commercially
CARAMELIZATION 1
1. Significance – about 11% of all colorants used; around 200 000 tons annual consumption
1850г. – used for the first time in Europe commercially
According to the FDA, “The color additive caramel is the dark-brown liquid or solid material resulting from the carefully controlled heat treatment of the following food-grade carbohydrates: dextrose, invert sugar, lactose, malt syrup, molasses, starch hydrolysates and fractions thereof, sucrose.”36
According to JECFA (The Joint FAO/WHO Expert Committee on Food Additives), “Caramel is a complex mixture of compounds, some of which are in the form of colloidal aggregates, manufactured by heating carbohydrates either alone or in the presence of food-grade acids, alkalis or salts; classified according to the reactant used.” 41
36. U.S. Food & Drug Administration, Summary of Color Additives Listed for Use in the
United States in Food, Drugs, Cosmetics and Medical Devices, Washington, D.C.,
1999.
41. JECFA, Combined compendium of food additive specifications,

3. !
CARAMELIZATION 2

4. CARAMELIZATION 3
2. Obtaining; phases
Raw materials – glucose, glucose-fructose syrup (HFCS), sugar, hydrolysates – corn, wheat, tapioca etc.
Chemical reactions involved – hydrolysis, enolization, dehydration, bonds (С-С) rupture, aldolization, cyclization, radical reactions
Requirements
Hue index –
Hue index = 10 log (A510 / A610)
 Initial caramelization temperatures of common carbohydrates
Sugar
Temperature
Fructose
110° C
Galactose
160° C
Glucose
Maltose
180° C
Saccharose

5. ! CARAMELIZATION 4 2. Obtaining; phases
I stage – anhydro sugars formation – 30 min ( ºС), 4.5% losses; dimerization – isosachrosan formation;
II stage – formation of caramelan – 50 min (180ºС), 9% losses
Soluble in water and EtOH; bitter taste; tm = 138ºС
III stage – formation of caramelen – 80 min (180ºС), 14% losses
Soluble in water; bitter-sweet taste; tm = 154ºС
IV stage – formation of caramelin (huminic type polymers) – 110 min (180ºС),
Slightly soluble in water; average composition С125Н188О80

6. 2. Obtaining; phases – caramelization of sucrose5
2. Obtaining; phases – caramelization of sucrose
Step
T, °C / 60 min
Description and use
Image 1
Evaporation of water
100
Sugar is melted and impurities rise to the surface; 2
Small Thread
102
No colour; soft cooling; no flavour change. Used in frostings. 3
Large Thread
104
No colour; soft cooling; no flavour change. Used in preserves. 4
Small Ball
No colour; semi-soft cooling; no flavour change. Used in cream candy fillings, Italian meringue, fondants, fudge, and marshmallows; 5
Large Ball
No colour; firm cooling; no flavour change. Used in soft caramels; 6
Light Crack
129
No colour; firm cooling; no flavour change. Used in semi-hard candies. 7
Hard Crack  
No colour; hard cooling; no flavour change. Used in butterscotch and hard candies;

7. 2. Obtaining; phases – caramelization of sucrose6
2. Obtaining; phases – caramelization of sucrose 8
Extra-hard Crack
168
Slight colour; shatters like glass during cooling; no flavour change. Used in hard candies; 9
Light Carmel
180
Pale amber to golden brown; rich flavour. 10
Medium Carmel
Golden brown to chestnut brown; rich flavour; 11
Dark Carmel
Very dark and bitter; smells burned. Used for colouring, but lack of appropriate sweetness; 12
Black Jack
210
Also known as "monkey's blood." At this point, the sugar begins to breaks down to pure carbon. Burning flavour.

8. CARAMELIZATION 7
2. Obtaining; phases
electronegative caramel (рН ) – obtained in acid medium, use of inorganic catalysts, 160ºС;
electropositive caramel (рН ) – obtained in presence of ammonia, ºС.
2.1. Obtaining of anhydro-sugars

9. CARAMELIZATION 8
2. Obtaining; stages
2.1. Obtaining of anhydro sugars

10. 5-methyl-2-(1-propenyl)-
CARAMELIZATION 9
2. Obtaining; stages
2.2. Obtaining of heterocyclic unsaturated compounds
5-methyl-2-(1-propenyl)-
furan
furfuryl
alcohol
α-angelica
lactone
5-methyl-2-
furanone
2-methyl-
tetrahydro-3-
furanone
2-furfural
5-methyl-
2-furfural
2-acetylfuran
2-propionyl-
furan
isomaltol
2-(2-hydroxy-
acetyl)-furan
5-HMF
2,5-diformyl furan

11. 5-(formyloximethtyl)-
CARAMELIZATION 10
2. Obtaining; stages
2.2. Obtaining of heterocyclic unsaturated compounds
5-methyl-2-
furylic acid
2-(2-oxo-
propionyl)furan
furfurylacetate
5-hydroxymethyl
2-furilic acid
5-methyl-2-(2-oxo-
propionyl)-furan
1-(2-furyl)-1,2-
pentandion
5-(formyloximethtyl)-
2-furfural
5-(acetoxymethyl)-
2-furfural
furaneol
formoin

12. 5-(5-methyl-2-furfuryl)-
CARAMELIZATION 11
2. Obtaining; stages
2.2. Obtaining of heterocyclic unsaturated compounds
cyclotene
maltol
5-hydroxy-5,6-
dihydromaltol
5-hydroxymaltol
5-(2-furfuryl)-
2-furfural
5-(5-methyl-2-furfuryl)-
2-furfural
2,2’-difurilketon
difurfurylether
bis-(5-formyl-2-furfuryl)-ether

13. CARAMELIZATION 12
2. Obtaining; stages
Some flavors present in the caramels
diacetyl (buttery flavor);
esters, lactones – rum flavor, sweetish
furans – roasted nuts flavor
maltol and isomaltol – caramel-like, sweetish, burnt (well-done)

14. CARAMELIZATION 13
2. Obtaining; stages
2.3. Obtaining of unwanted heterocyclic unsaturated compounds
- 4-methylimidazole (4-MeI) - Neurotoxic effects
2-acetyl-4(5)-tetrahydroxybutylimidazole (THI)
Immunosuppressive effects
2.4. Polymerization – aldol condensation reactions

15. ! CARAMELIZATION 14 3. Application – mainly as food additive Parameter
Type I (E 150a)
Type II (E 150b)
Type III (E 150c)
Type IV (E 150d)
Sulfites no
yes
Ammonia compounds allowed
Catalysts
NaOH
Na2SO3
NH3
(NH4)SO3
Charge -
negative
positive
Stability in:
Alcohol
Tannins
Acids +
Hue
Yellow-orange
Brown
Application
Alcoholic beverages, coffee extracts
Aperitives and digestives, aroma extracts
Beer, vinegar, sauces
Fizzy drinks, some foods

16. CARAMELIZATION 15
3. Application – mainly as food additive

17. CARAMELIZATION 16
3. Obtaining

18. CARAMELIZATION 17
Interactions with other substances
Over 700ppm – could lead to aspartame hydrolysis.
Adulteration of juices, coffee, honey.
Caramelization could be regarded as part of the Maillard reaction and as separate reaction.
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