SYNTHESIS AND SOME REACTIONS OF POLYOLS FORMALS
Scheme 6.
Scheme 7.
5
H
H
H
7
6
7
6
+
5
5
4
9
9
O
O
8
8
4
O
O
H
O+
m/z = 73
O
O
O
O
O
O
O
O
O
2
2
1
1
m/z = 87
R(S)
R(S)
R(S)
S(R)
11a
11b
From the integral intensity of the protons of the С4Н
group, the ratio of the isomers 11а : 11b is 6 : 5.
40 mL of benzene (in the case of dipentaerythritol the
mixture of DMF and benzene) was stirred at 80°С for 3–
8 h until the calculated amount of water was evolved.Af-
ter completion of the reaction, the mixture was dried with
CaCl2, filtered and evaporated on a rotary evaporator. The
reaction products were isolated by vacuum distillation.
In the 13С NMR spectra of formals of diglycerol 11а,
11b the signals of atoms С4 and С8 appear at 70.3 (11а)
and 74.2 ppm (11b). The signals of carbon atoms С2 and
С11 of the 1,3-dioxolane ring are observed at 93.3 (11а)
and 95.1 ppm (11b). The signals of the ether group С6 and
С7 are registered at 66.2 ppm (11а) and 69.9 ppm (11b).
Oxybis(methylene-1,3-dioxane-5,5-diyl)dimetha-
nol (5а). Mass spectrum, m/z (Irel, %): 159 (10), 147 (60),
129 (25), 99 (100), 87 (10), 69 (60), 57 (20), 41 (60).
Ionization of diglycerol formals 11а,b proceeds with
the formation of the same fragment ions differing only
in the intensity (Scheme 7). For the erythro-isomer 11а,
maximum intensity is observed for ions with m/z = 87 and
73, whereas for the treo-isomer 11b maximum intensity
(100%) has only the ion with m/z = 87. The molecular
ion with m/z = 190 is more stable in isomer 11a (5%),
whereas its intensity in the treo-isomer 11b is 1%.
Oxybis(methylene-1,3-dioxane-5,5-diyl)dimetha-
nol (5b). Mass spectrum, m/z (Irel, %): 159 (12), 147 (30),
129 (20), 99 (60), 87 (100), 69 (75), 57 (10), 41 (30).
5,5-[Oxydi(methylene)]bis(5-ethyl-1,3-dioxane)
(6а). Mass spectrum, m/z (Irel, %): 274 (2) [M+·], 147 (90),
129 (50), 99 (96), 69 (96), 57 (75), 41 (100).
5,5-[Oxydi(methylene)]bis(5-ethyl-1,3-dioxane)
(6b). Mass spectrum, m/z (Irel, %):274 (1) [M+·], 147 (45),
129 (25), 99 (94), 69 (80), 57 (80), 41 (100).
Therefore, we have synthesized formals of dipentae-
rythrol, diglycerol, and di(trimethylol propane), whose
structure was analyzed by the methods of NMR spec-
troscopy and chromatomass spectrometry. On the basis
of formal of dipentaerythrol, the esters and carbamates
were synthesized.
4,4-[Oxydi(methylene)]bis-1,3-dioxolane (11а).
Mass spectrum, m/z (Irel, %): 190 (5) [M+·], 189 (3), 117
(12), 101 (3), 87 (100), 73 (100).
4,4-[Oxydi(methylene)]bis-1,3-dioxolane (11b).
Mass spectrum, m/z (Irel, %): 190 (2) [M+·], 189 (1), 117
(3), 101 (2), 87 (100), 73 (53).
EXPERIMENTAL
Chromatography analysis of the reaction products was
carried out on a HRGС 5300 Mega Series Carlo Erba chro-
matograph with flame-ionization detector (gas-carrier—
helium, 30 mL/min, column of 25 m length, temperature
programming mode with heating from 50 to 280°С with
the rate 8 deg/min). Mass spectra were obtained on a
Crystal-5000 М instrument (gas-carrier—helium, capil-
lary column of 30 m length, column temperature from 80
to 280°С with the rate 20°С/min, temperature of the tran-
sition line 300°С, temperature of the ion source 300°С).
NMR spectra were registered on a BrukerAVANCE-500
spectrometer (1H 500.13 MHz) in CDCl3.
General procedure for the synthesis of esters (8а,
8b). The mixture of 0.03 mol of dipentaerythritol formal,
0.03 mol of dry pyridine and 0.03 mol of chloroacetyl
chloride was heated to 30°С for 1 h. The reaction mixture
was kept in the fridge for 1 day, then poured into the
mixture of 15 g of ice and 30 mL of 1 M HCl and stirred
until the formation of suspension. The crude product
was filtered and crystallized from isopropanol. The ratio
8а : 8b = 3 : 1.
Oxybis(methylene-1,3-dioxane-5,5-dimethylene)-
bis-chloroacetate (8а). Mass spectrum, m/z, (Irel, %):
(276/278/280)/(3/1/0.4), (207/209)(30/10), 147 (31),
(99/101)/(34/12), 83 (100), 55 (30).
General procedure for the synthesis of formals of
dipentaerythritol (5а, 5b), di(trimethylol propane) (6а,
6b), and diglycerol (11а, 11b). The mixture of 0.02 mol
of alcohol, 0.06 mol of paraform, 0.2 g of sulfuric acid,
Oxybis(methylene-1,3-dioxane-5,5-dimethylene)-
bis-chloroacetate (8b). Mass spectrum, m/z, (Irel, %):
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 90 No. 1 2020