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Chemical Properties and Derivatives of Glycerol PDF
Chemical Properties and Derivatives of Glycerol PDF
n
By varying the amounts and kind of modifying mono
acid, the resin chemist can develop a product to suit a
virtually limitless range of coating requirements. The
REDUCTION glycerol can also be reacted with a number of polybasic
Catalytic Hydrogenation acids rather than the commonly used phthalic acid to
Glycerol is easily reduced to propylene glycol (1,2,- produce resins with specific properties for particular
dihydroxypropane) with hydrogen at pressures from 10 applications.
to 100 atmospheres and temperatures above 150° C . There are five general reactions for the preparation of
Many catalysts may be used, e.g., Ni, Fe, Pt, Au, Hg, glycerol esters:
copper chromite or tungstic acid(21). CSHs(0H)r
glycerol
++ RCOOH
acid
= CaHs(0H)rOOCR + Hz0
(esterification)
(1)
Cm
I
CHOH -+ CHOCOR--+CHOCOR
CH-OH CH-0-PO
(OH),
I
CH2-OH LH2-OH Borax (Na2B,0,.10H20) added to glycerol in water
a-isomer R-isomer solution becomes acid. The borax dissociates and the
same glycerol-boric acid compound is formed that is
This, and more particularly its salts of ammonium, obtained with boric acid(72).
calcium, iron, potassium and sodium, are used in pharm-
aceutical preparations and soft drinks. Esters of glycerol ETHERS
phosphoric acid occur widely in nature, especially in Glycerol can form mono-, di-, and triethers. They
lecithin, and the products of animal carbohydrate metab- may be either ethers of glycerol with itself (polygly-
olism. For a review of the literature and a discussion of cerols), inner ether (glycidol), o r mixed ethers of
the structure and solubility of the salts of glycerol glycerol with other alcohols.
phosphoric acid see DuBois, Inc. & Eng. Chem. 6, 122-
128 (1914). Polyglycerols
Esterification of glycerol with phosphoric acid at For the commercial production of polyglycerols, gly-
100° C. under normal pressure produces mainly the cerol is heated with an alkaline catalyst at elevated
alpha isomer. If the glycerol is esterified by heating with temperatures (200" C. -275" C.) at normal or reduced
sodium dihydrogen phosphate the beta isomer is the pressure. A stream of inert gas may be used to blanket
principal product. The two isomers are interconvertible the reaction and help remove the water of reaction.
in acid solution but stable in the presence of alkali. There are many patents and disclosures covering varia-
The proportion of alpha and beta isomers can be tions of these factors, but the essentials remain the same.
estimated by treatment with periodic acid. This will How well the process steps are applied and utilized
quantitively oxidize the alpha isomer and not affect the appears to make the difference in the quality of the
beta.(r4) products produced. Light color, good odor, and flavor
Esters other than glycerol monophosphoric acid can are essential for the many edible and industrial appli-
be prepared by suitable changes in the temperature and cations that are contemplated. The polyglycerols are
concentration of the reactants. Glycerol phosphoric similar to glycerine but offer greater flexibility and func-
acids may also be prepared by the reaction of chloro- tionality. In the homologous series of polyglycerols,
hydrins with di-, or trisodium phosphate, glycerol with their molecular weight and the number of hydroxyls can
disodium phosphate, epichlorohydrin with phosphoric increase thus providing versatile polyols which can offer
advantages per se or through the derivatives that may glycerols depending on the type and amount of the
be synthesized. fatty acids used. Hydrophilic to lipophilic properties
In the series of polyglycerols which are produced by can be built into the structure by varying the number of
this method some unchanged glycerine will remain in free hydroxyls.
the mixture. The resulting products are mixtures of a
range of molecular weights but averaging out to a mean Polyglycerol Esters
molecular weight of diglycerol, triglycerol, etc. The Polyglycerol esters have been prepared from the
application of vacuum (stripping) to remove the free various polyglycerols available. Partial and complete
glycerine is helpful in narrowing the range of molecular esters of saturated and unsaturated fatty acids form a
weights in the resulting product. The hydroxyl value, variety of derivatives of polyglycerols ranging from
viscosity, refractive index, and the amount of water diglycerol (2 moles) to triacontaglycerol (30 moles).
removed in the reaction are used as controls in the pro- Partial esters of polyglycerols may be prepared by (a)
duction of consistent products. direct esterification and (b) transesterification reactions.
In the formation of polyglycerols, an ether linkage The variations in molar ratios of the fatty acid or the
for every 3 carbon atoms results with the splitting off oil will determine the formation of mono-, di-, or poly-
of water. This unit is repeated as the polymer chain ester from the respective polyglycerol.
increases. Completely esterified products may be prepared from
Table I gives some physical constants and the theo- a given polyglycerol by using excess amounts of the
retical hydroxyl numbers for products having the indi- fatty acids in the esterification reaction.
cated average composition. Table 111, (a), ( b ) and (c), gives some constants of
TABLEI. SOMEPHYSICAL
AND CHEMICAL CHARACTERISTICS O F POLYCLYCEROLS
Molecular Number of Calculated Found Viecoaitiea CTKS
Compound Weight OH Groups OH Value OH Value @ 160'F @ 180°F
Glycerol ..............
Di-gl ycerol ...........
Tri-gl ycerol ..........
Tetra-gl ycerol.........
Penta-gl ycerol ........
Hexa-glycerol .........
Hepta-glycerol
Octa-glycerol
........
..........
Nona-gl ycerol .........
Deca-glycerol .........
Penta deca-glycerol ....
Triaconta-glycerol .....
Polyglycerols ranging from diglycerol to triacontagly- typical polyglycerol esters which are in commercial pro-
cerol have been prepared. The polyglycerols range from duction and being used in foods, pharmaceuticals, cos-
viscous liquids to solids. They are soluble in water, metic preparations, and other industrial applications.
alcohol, and other polar solvents. They act as humec- Table IV, ( a ) , ( b ) and ( c ) , gives some constants of
tants much like glycerine but have progressively higher typical polyglycerols which have been completely esteri-
molecular weights and boiling points. The polyglycerols fied. In essence such products are polymer oils and serve
as a homologous series of polyols are valuable inter- as high molecular weight functional fluids and solids.
mediates. Table I lists the polyglycerol types available
for esterification and their molecular weight range. Derivatives of polyglycerols are not limited to their
Products which are based on polyglycerols are useful as fatty acid esters. Reaction products of hydroxy acids,
surface active agents, emulsifiers, plasticizers, adhesives, ethylene oxide, propylene oxide, isocyanates, etc. have
lubricants, and other compounds which are utilized in been reported. These products show apparent applica-
both edible and industrial applications. tion in foods, pharmaceuticals, and cosmetic prepa-
rations.
Polyglycerols and polyglycerol esters are utilized by The polyglycerols and polyglycerol esters are now
the body and broken down to glycerine and fatty acids. available in such quality and variety that it is quite pos-
Food and Drug approval for polyglycerol esters up to sible that their application and use will show consider-
the decaglycerol esters has been granted in the United able growth in the next few years. It is one of the poten-
States, and across the board clearance has been given to tial outlets for glycerine and glycerine derivatives that
such compounds in Great Britain. Compounds varying has been a sleeping giant coming to life. An indication
from water to oil solubility can be produced from poly- of the areas of application is illustrated in Table 11.
POLYGLYCEROLS . . . . . POLYGLYCEROL ESTERS
I LUBRICANTS URETHANE INTERMEDIATES FUNCTIONAL FLUIDS I
PLASTICIZERS ADHESIVES SURFACE ACTIVE AGENTS
CROSS LINKING AGENTS
PAINT & VARNISH VEHICLES HUMACTANTS DISPERSANTS
I GELLING AGENTS TEXTILE FIBER FINISHES EMULSIFIERS
Chemical Identity
Color
Cardner
Hydroxyl
Value
Sap.
No. 2. FFA F O T ~ spec.
Grav. Melting
Point
pH %mono %free
A No. No. OK No' (3% 801) Glyceride Cbcerlne IV
3-Mono cottonseed oil .. 6.2
%Mono palm oil ... . . . 5.4
.
5-Di tallow oil .. . . . ... .. 4.8
3-Mono shortening oil
-
5-Di shortening oil
6-Sesqui palm oil
. . . . 1.8
..... 0.6
6-Di shortening oil
6-Di cottonseed oil
........ 4.4
7.0
6-Di peanut oil . .. . ... 4.8
9-Tri peanut oil . ... ... 5.6
9-Tri shortening oil
10-Mono corn oil
... 6.0
... . . . 7.4
10-Di shortening oil
10-Di palm oil
... 0.4
. ..... .. 2.0
10-Tri peanut oil ... . .. 7.6
10-Tri cottonseed oil . .. 7.2
10-Tri shortening oil
10-Tetra cottonseed oil
... 5.2
6.6
10-Penta cottonseed oil . 6.4
10-Penta shortening oil
30-Deca peanut oil ... .. 6.8
5.6
TABLEI I I ( c ) . ESTERSFOR THE PAINT,VARNISHAND URETHANEINDUSTRY
HydroxI Iod. Vise. @ 16S0F Color
Chemical Identity A No. Sap. No. Value Val. CPS Gardner
Triglycerol Monolinoleate
Triglycerol Pentalinoleate
Triglycerol Monolinolinate
Triglycerol .5 linoleate
Triglycerol Trilinoleate
Triglycerol Tetraricinoleate
Triglycerol .75 Ricinoleate
Triglycerol .5 Ricinoleate
Hexaglycerol .87 linoleate
Hexaglycerol 1.7 linoleate
Hexaglycerol .87 Ricinoleate
Hexaglycerol 6.6 Ricinoleate
Hexaglycerol .6 Ricinoleate
Hexaglycerol .8 Ricinoleate
Decaglycerol .9 Ricinoleate
Decaglycerol .8 Ricinoleate
Decaglycerol Decalinoleate
Decaglycerol Trilinoleate
Decaglycerol Dilinoleate
Decagl ycerol Monoricinoleate
Triglycerol 1.5 adipate
Triglycerol 1.7 adipate
Triglycerol Monoadipate
TABLEI V ( a ) . TRIGLYCEROL
SIMPLEESTERS
Viscosity CPS. Brookfield
Acid A No. Sap. No. S~oke FFh ?re Sp. Gr. Spindle No. 1 69°C
F F F Z6/l6'C 6 RPM 12 RPM 30 RPM 60RPM
.12
428.7
378.7
275
290
485
410 .
--
530
440
-
-
1.010
-.
6
7
- -
9.5
10
~
10.8
11.2
. 12.4
12.5
2-ethvlHexanoic ....... .90 261.3 305 465 480 0.978 11 13.5 15.2 16.5
-
iso-octanoic ........... 1.40 147.5 305 480 510 0.982 20 21.5 22.2 23.0
iso-decanoic ........... 1.00 279.1 335 495 540 0.959 22 23 25 26.5
2-ethylButyric ........ .30 312.7 265 445 485 1.009 36 36.5 33.0 30.7
Acetic
Isopentanoic
... ..............
..... . . .. .7
.20
584.1
388.6
225
305
445
465
465
485
-
1.051
67
17
72
18.5
73
21
73.6
21.8
2-methyl Pentanoic . . ... 1.3 351.6 240 405 430 1.029 19 20 21.2 22.6
Caprylic . . . . .. . ..... .. .08 311.9 - 510 535 .988 20 20.5 23.0 24.5
2-ethyl Hexanoic . .. . . .. .I8 267.2 305 485 500 .988 25 25.5 27 27.7
Pelargonic .... . ... . ... 1.6 293.9 360 520 550 .983 25 25 26 26.8
2-ethyl. Butyric
isb-decanoic
. .. .....
...........
1.0
.10
318.2
267.6
300
320
460
510
485
550
.988
.981
30
38
32.5
40
34
41
35.5
42.4
iso-octanoic ........... .40 304.1 325 500 525 .999 40 42.5 43.2 44.5
o.,l
i I
r (-s
B. r (4c/m) sTjly ";
-
Sol in
soln
00
CH
I
I
/O
+ R-OH H+ or OH-
I
CH-OH
I
-CHI-OH
CHz-OH
00 When dichlorohydrin is used, two epoxy rings are
successively formed and opened and a diether is pro-
00
duced(92).
00 An alternate method of producing glycerol ethers is
the reaction of sodium glyceroxide with an alkyl or aryl
m
00
bromide or alkyl sulfate.(93) ~ l ~ c e r oethers
l may be
prepared from glycidol, epichlorohydrin or a glycidol
00
ether by treatment with an alcohol or a phenol. The
10
reaction is catalyzed by either acid or alkali'94).
The glycerine molecule can react with other alcohols
8 to form aliphatic or aromatic ethers, or as pointed out
20 before with itself to form polyglycerols as:
CHrOH.CHOH-CHfOH
glycertne
NaOH
-------
23OoC.
+ (CHzOH-CHOH-CHI),,O
polyelycer~nes
1
CHtOH-CHOH-CH?OH
glycerine
+ CIHIIOH
lsoamyl
------ 3 CIHII-0-CHYCHOH-CH4H
glycer~nealphamono~soamyl
+ Hz0
1 alcohol ether
GLYCEROL AMINES
Glycerol amines are formed by ihe replacement of
one or more of the hydroxyls by amine groups. They
are basic compounds, generally water soluble and hy-
groscopic. With fatty acids they form soaps that are sol-
uble in organic solvents(g7). The glycerol mono-, and
diamines are readily made from the corresponding u,&Methylidene Geometric
glycerol isomers
chlorohydrins or bromohydrins, while the triamine is
usually prepared from non glycerol origins.
When a glycerol halohydrin and ammonia react, it is The two geometric isomers of each of the structural
possible for a number of products to be formed. Each of isomers of para-nitro benzylidene glycerol were isolated
the ammonia hydrogens can react, so mono-, di-, and by Hibbert and Sturrock(lo7)but their configuration was
triglycerol amines can be formed. If a dihalohydrin is not established. The geometric isomers of alpha, gam-
used, the number of possible products is increased by mabenzylidene glycerol were separated by Verkade and
the opportunity for the formation of long-chain mole- van Roon(lo8).
cules and cross-linkages. Insufficient ammonia favors the The principal method of preparing glycerol acetals is
formation of such complex products. They are non- by the condensation of glycerol with an aldehyde or
volatile and vary from viscous liquids to more or less ketone in the presence of an acid or an acid salt. If the
solid materials(g8). The preparation of simple glycerol carbonyl compound is comparatively cheap as compared
amines, the diamines and the triamines is described in with glycerol, or may be easily removed, it is ordinarily
several sources(99,lOO."31. 102,103,104). used in large excess, as much as 4 or 5 moles to 1 mole
of glycerol. Various acids and acid salts have been tried
GLYCEROL ACETALS as catalysts. Hydrochloric acid or sulfuric is frequently
used, the amount being in the order of one percent or
The acetals of glycerol, formed by the condensation
less based on the glycerol.
of glycerol with aldehydes and ketones are heterocyclic
Glycerol and other alcohols can be converted into
compounds that show structural, geometric and optical
acetals by combination with vinyl ethers, preferably in
isomerism. They are formed by the condensation of two
the presence of an acid catalyst and in a solvent such as
hydroxyls of a glycerol molecule with the carbonyl of
ether or c h l o r o f o r m ~ ~ 0 ~ ~ .
an aldehyde or a ketone. The reaction is catalyzed by
The ease with which acetals are formed is influenced
acid and is an equilibrium reaction, sensitive to the pres-
by the polar character of the carbonyl group. As it be-
ence of water. These isomers have been very thoroughly - -
shdied(84, 105). comes more negative, the ease of formation and the
stability of the intermediate product (a hemiacetal) in-
CHrOH or creases but the completion of the reaction with closure
I R CH-OH 'C + H20 of the ring becomes more diflicult(llO* lo6).
CH-OH +o=c: R
I " l
(1) (II)
Temperature plays an important role in determining
the ratio of isomeric acetals formed. I t is believed the
ring fission occurs under the influence of the acid cata-
lyst and that the reaction then goes to equilibrium, which
OME GLYCEROL
ACETALS
Nuns
I Formula B.P. *C/mm I d (*C)
alp-Methylidene glycerol
aI7-Methylidene glycerol
~,p-Ethylideneglycerol
a, 7-Ethylidene glycerol
a#-Propylidene glycerol
aI7-Propylidene glycerol
a,p-Ieopropylidene glycerol
a , y-Ieopropylidene glycerol
a,P-Benrylidene glycerol
a,y-Benaylidene glycerol
a$-p-Nitrobenzylidene glycerol
a , y-p-Nitrobenzylidene glycerol
Melting point.
The physical properties of some of the acetals of The reaction is the basis of several quantitative tests
glycerol are given in table 4. Only structural isomerism for glycerol. Acrolein and aldehyde condensation prod-
is considered here. ucts are formed when glycerol vapors are passed over
Acetals and ketals of glycerine have applications as alumina a t 360° C. Finely divided copper a t 330° C.
solvents and plasticizers and since they are easily hydro- causes glycerol to decompose to acrolein, ally1 alcohol,
lyzed are a potential source of reactive groups. ethyl alcohol, hydrogen and small amounts of carbon
monoxide. Other catalysts will cause breakdowns of
DEHYDRATION AND PYROLYSIS glycerol to the above products in different proportions.
Glycerol is also fermented to acrolein by B. amaracry-
Dehydration of glycerol may form a number of prod- lis, the organism which produces bitterness in wine.clll)
ucts, but the principal is acrolein -
COMPOUNDS WITH BASES AND SALTS
Glycerol reacts readily with alkalies, alkaline earths
1 heat
and some metallic oxides to form glyceroxides which are
analogous to the alcoholates, and are generally stable
only in the presence of an alkali. Lead glyceroxide,
CH2 = CH-CHO + 2H20 formed from litharge and glycerol, is relatively insoluble
and stable.
+
C3H5(OH) 3 NaOH # C3H5(OH) *ONa H 2 0 +
This in turn reacts with cupric hydroxide.
The reaction is exothermic. Although amorphous at 2C3H5(OH) ,ONa + Cu (OH), e
first, the compound soon changes to minute fibrous cry- +
[C3H5(OH) 2 0 ],CU 2NaOH
I stals which radiate from the particles or unreacted Thus glycerol can be substituted for sodium-potas-
litharge and bind the whole into a very hard mass(112- sium tartrate in Fehling's solution(126'.Complex com-
113). The percentage of water, pH, and freshness of the pounds containing two metals such as barium, strontium,
litharge all affect the rate of hardening of the cement. calcium, iron, aluminum, chromium, antimony or bis-
(90. 114, 115)
muth may be prepared from glycerol, alkali and the
When glycerol reacts with bases and salts either an appropriate metal salt,(127-12*, 129).
alpha or beta hydroxyl group may react, but the former When a solution of a copper salt, except cupric
reacts more readily cH6). chloride, in glycerol is heated to 150-200° C., a vigorous
Sodium glyceroxide is easily prepared by heating and reaction occurs and finely divided metallic copper is
stirring together equimolar quantities of powdered sod- produced. The copper is suitable for use as a catalyst.
ium hydroxide and glycerol. The reaction is exothermic With cupric chloride, crystalline cuprous chloride is
and becomes very rapid at temperatures above about produced (130).
140° C.
91. BAER,E.. FISCHER,H. 0. L. and RUBIN,L. J., J. Biol. TRAUBE,and ~(UHBIER, F. (to Winthrop Chemical Co.)
Chem.. 170, 337-342 (1947). U. S. Pat. 1,990,442 (Feb. 5, 1935).
KARNOVSKY, M. L. and RAPSON, W. S., I . Soc. Chem., Ind., VAIDYA, B. K., Nature, 123, 414 (1929).
65, 138-140 (1946). ZIENER,Th., Sprechsaal. 72. 270-272 (1939).
92. FAIRBOURNE, A. and FOSTER,G. E., J . Chem. Soc., 127, SCHOOL, R. & 'MEYER, H. K., Ber., 69B, 152-158 (1936).
2759-2764 (1925); 1930, 369-382; 1932, 1965-1972. BALLY.0. and SCHOOL.R.. Ber.. 44. 1656-1670 ( 19481.
93. CROSS,C. F. and JACOBS,J. M., J. Soc. Chem. Ind., 45, BABAYAN, KAUNITZ and S ~ A N E T Z - N U ~ ~ ~ studies
~ ~ O ~ ~with
I
320-321 (1926). Polyglycerol Esters. Presented at AOCS meetings in
DANILOV.S., DRYAKHLITZUINA. V., MANOKHIMA, 0. and Atlanta, Ga., April 22, 1963. (In Publication).
ORLOVA, N.. Plasticheskia Massui, 1934, No. 2, 11-16. NASHand B A B A Y A N - P Esters-Their ~ ~ ~ ~ ~ ~Chemistry,
c ~ ~ ~ ~
94. BOYD,D. R. and MARLE,E. R., J. Chem. Soc., 93-4, 838- Status and Use in Bakery and Other Food Products.
842 (1908); Proc. Chem. Soc., 24, 92 (1908). Presented at American Association of Cereal Chemists,
FOURNEAU,E. and RIBAS,L.. Bull. SOC.chim.. ( N )39, Minneapolis, Minn., April 30, 1963.
1584-1589 f 1926).
-- - - - BABAYAN, KAUFMAN, LEHMAN and TKACZUK-Po~yglycero~
LEFEBURE, 'H.. LEVAS. E. and LEVAS,Mme. E., Compt. Esters-Some Uses and Applications in Cosmetic & Phar-
rend., 222, 1439-1440 (1946). maceutical Preqarations. Presented at Society of Cosmetic
LEVAS.E.. and LEFEBURE, H., Compt. rend.. 222. 555-557 Chemists, New York, N. Y., Nov. 6, 1963. (In Publication).
(1946). BABAYAN, LEHMAN and WARMAN-Polyglycerolsand Poly-
LINDEMAN, Thv., Ber., 24, 2145-2149 (1891 ). glycerol Esters-Some Typical Derivatives and Applica-
MARLE,E. R., I. Chem. Soc., 101, 305-307 (1912); Proc. tions. Presented at ACS meetings in Philadelphia. Pa.,
Chem. Soc. 28, 5 (1912). April 6. 1964. (In Publication).
MARPLE,K. E. and EVANS,T. W. (to Shell Development F.D.A. approval date notices-Federal Register March 19.
Co.) U.S. Pat. 2,321,037 (June 8, 1943). 1963, Doc. 63-2833 and July 2. 1963, Doc. 63-6933.
95. SMITH,L. and SJOBERG,B., Ber., 69B, 678-680 (1936). Drew Foods Co. Bulletin No. FE-3.
S u r r o ~ ,L. E., I. Am. Med. Assoc., 104, 2168-2171 BODANSKY et al., Biochem. J. 32, 1938-1942 (1938).
(1935). , British Food Regulation. Statutory Instruments 1962,
96. RHEINBOLDT, H. and TESCH,C., Ber., 708,675-680 (1937). No. 720.
97. FAIRBOURNE, A., GIBSON,G. P, and STEPHENS,D. W.,
Chemistry & Industry. 49, 1069-1070 (1930).
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I
CONTENTS
Catalytic Hydrogenation ...................................... 4 Glycerol Butyrates .............................................
Characteristics & Nomenclature .......................... 2 Glycerol Caproates ..............................................
Chlorohydrins...................................................... 7 Glycerol Carbonates ............................................
Compounds with Bases and Salts ........................16. 17 Glycerol Formates ................................................
Bromohydrins ...................................................... 8 Glycerol Nitrates ..................................................
Decomposition When Heated with Caustic .......... 3 Glycerol Nitrite ....................................................
Dehydration and Pyrolysis .................................. 16 Glycerol Oxalates ................................................
Epichlorohydrin .................................................. 13 Glycerol Pripionates ............................................
Epibromohydrin .................................................. 13 Glycerol Valerates ..............................................
Epoxy Compounds ............................................... 13 Glycidol .................................................................
Esters of Amino Acids ........................................ 5 Iodohydrins ..........................................................
Esters of Arsenious Acid .................................... 9 Oxidation ............................................................
Esters of Boric Acid ............................................ 9 Oxidation with Bromine ......................................
Esters of Higher Fatty Acids ................................ 5 Oxidation Catalyzed by Radiation ...................... 3
Esters of Hydroxy Acids ....................................... 5 Oxidation with Dichropate and Permanganate .... -3
Esters of Inorganic Acids (Halohydrins) ............ 7 Oxidation by Electrolysis .................................... 3
Esters of .Organic Acids ...................................... 4 Oxidation with Oxygen ........................................ 3
Esters. Phosphoric Acid ...................................... 10 Oxidation with Hydrogen Peroxide ...................... 3
Esters of Sulfuric Acid ........................................ 8 Oxidation with Lead Tetraacetate ...................... 3
Ethers ................................................................ 9. 1 0 Oxidation with Periodic Acid .............................. 3
Ethers of Glycerol. mixed ....................................13. 14 Oxidation with Salts ............................................ 3
Glycerides ............................................................ 6 Photochemical Oxidation .................................... 3 . 4
Glycerides by Esters Interchange. preparation of 6. 7 Polyglycerols ....................................................... 9. 10
Glycerides of Known Structure. preparation of .... 6 Polyglycerol Esters ............................................ 10
Glycerol Acetals .................................................15. 16 Reduction ............................................................ 4
Glycerol Acetates ................................................ 5 Reduction with Hydriodic Acid .......................... 4
Glycerol Amines .................................................. 15 Sulfur Compounds ..............................................
14, 15
Glycerol Benzoates .............................................. 5. 6