DD139852A1 - PROCESS FOR PREPARING CRYSTALLINE-FLUID SUBSTITUTED 1,3-DIOXANES - Google Patents

Abstract

The invention relates to a process for the preparation of novel crystalline liquid 1,3-dioxane derivatives which can be used in optoelectronic components. The object of the invention is the preparation of crystalline-liquid substituted 1,3-dioxanes. It has been found that crystalline 2,5-disubstituted derivatives of 1,3-dioxane of general formula I can be prepared by reaction of alkanals, substituted benzaldehydes or their acetals with glycerol or 2-substituted propanediols (1,3) in organic solvents in the presence of an acidic catalyst according to the general scheme (formula II) and optionally esterified or etherified. Formulas I and II

Description

-A-

Process for the preparation of crystalline-liquid substituted he 1,3-dioxane

Applicability of the invention

The invention relates to a process for the preparation of crystalline liquid substituted 1,3-dioxanes which, owing to their favorable properties, e.g. can be used in optoelectronic components.

Characteristics of the known technical solutions

The substances produced by the process according to the invention are novel and processes for their synthesis have hitherto not been known.

Object of the invention

The object of the invention is the preparation of crystalline-liquid substituted 1,3-dioxanes.

We exposition of the sens of the Invention 'It has been found that liquid crystalline-2,5-disubsti-. tuted. Derivatives of 1,3-dioxane of the general formula

in which

-2- 209 7i

X *

or X «R or X -H such as

mean,

and Y

and Y = IT- ^; and Y = R--

^C n ^H 2n ₊ 1 ^{0 'C} n ^H 2n ₊ 1 ^COO 5 R ⁴ - {h) -C00; C _n H _{2n + 1} OCOO; C _n C _n H _{2n + 1} (CH ₃ ) N; -CNj NO ₂ ; Fj Cl; bt; NC-CH = CH; NC-CH ₂ -CH ₂ ; NC-CH ₂ ,

» ^CN J ^or4 > OCOR ⁴ ; OCOOR ⁴ ; OCO- ⁴

OCO- <j7) -R ⁴ J

^r4 - ^C n ^H 2n ₊ 1

with η «1 to 10,

can be prepared by reaction of alkanals, substituted benzaldehydes or their acetals with glycerol or 2-substituted propanediol (1.3) in organic solvents in the presence of an acidic catalyst according to the general scheme:

X - CHO +

CH - Y

and which may still be esterified or etherified.

-m 3

example 1

Preparation of the 2-alkyl-propanediols (i, 3) (see Table 1) and the 2- / 4-Substituted-phenyl-7-propan-aiols (- l, 3) (see Table 2) 21 g (0.5 mol) of LiAlH 2 in 1 l of absolute ether are placed in a 2 l three-necked flask, with ice cooling and vigorous stirring, 1 mol of n-alkylmalonic ester or 1 mol of 4-substituted phenylmalonic acid ester. Ether is mixed with the same volume of absolute ether, added slowly and then stirred for a further 2 hours at room temperature, then 100 ml of ice water are added carefully to the resulting precipitate (Al (OH), LiOH) by addition of 700 ml The organic phase is separated off, the aqueous phase is extracted twice, and the combined organic phases are washed with 2% NaHCO 3 solution and water, after which, after drying with Na 2 SO 4, the solvent is dissolved in water Vacuum distilled off and the Rüokstand fractionally distilled Examples are given in Tab. 1 and 2.

Table 1

η yield ($>) kp / mrn

3 63 92-93 / 2.5 4 69 107-110 / 2 5 65 125-126 / 2.5 6 73 133-136 / 2.5 7 75 Ti 28-30 (petroleum ether) 8th 74 F: 44-46 (petroleum ether)

Table 2

yield

^C 6 ^H 13

75 89

72-74 70-72

Example 2:

Production of the connections 1_, 2, 3_

0.1 mol of alkaual or 0.1 mol of substituted benzaldehyde or acetals thereof and 0.11 mol of 2-alkyl-propanediol (i, 3) or 0.12 mol of glycerol or 0.11 mol of 2 ~ </ ~ 4 -Subst.-phenyl_7-propanediol- (i, 3) are in 150 ml of abs. Benzene, chloroform, methylene chloride, carbon tetrachloride or toluene in the presence of 100 mg of p-toluenesulfonic acid or AlCl-j, SbCl 2,

_{Heat 4} or 2 ml of a mineral acid (HCl, H ₂ SO ₄ , H ₅ PO ₄ ) with stirring on a water separator until the reaction is complete. While cooling the reaction mixture is washed with 2% NaHCO, solution and water and dried over Na ₂ SO ₄ . The solvent is distilled off on a rotary evaporator and the residue is recrystallized from methanol. The yield is about 80 - 100 % of theory. Examples are summarized in Tables 3, 4 and 5.

In the tables: K "crystallin-solid, S., _Sβ = smectiscli A" or B, N »nematic, I = isotropic-liquid,

Table 3

H ¹ -

^x o- /

Yeth. R

^ A

, N

HO

C ₇ H

₁₅

.107-109 - - - -.

1.2 C ₄ H ₉ C ₃ H ₇ • ^S B 26 (· - 25) 1.3 C ₃ H ₇ O ^C 4 ^H 9 , 43 - (· - 40) C ₄ H ₉ O " C ₄ H ₉ , 44 - - C. - 35.5) C ₅ H ₁₁ O C ₄ H ₉ , 49 - - C- C 43) C ₆ H ₁₃ O ^C 4 ^H 9 , 31 - · - C 41.5) C ₇ H ₁₅ O ^C 4 ^H 9 , 45 - c · 45) C ₉ H ₁₉ O ^C 4 ^H 9 , 47 - - (. 35 * 5)     ι jS.i ι CN ^C 4 ^H 9 , 42 - - * 40 _o 5 1.10 C ₃ H ₇ P ^C 5 ^H 11 , 37.5 C 28.5) 53 : bdl C ₄ H ₉ O C ₅ H ₁₁ , 40 - * 50.5 C ₅ H ₁₁ O S ^H 11 • 38- C 29) 56 ii | ^C | Ji T__ C ₆ H ₁₁ O C ₅ H ₁₁ , 44 (. 22). * 55 jg_14 C ₇ H ₁₅ O C ₅ H ₁₁ , 45 C 34) • 56.5 1.15 C ₉ H ₁₉ O K * \ -A , 48 C- 41) 48) 1.16 ' CK , 55 - _ ULL C ₃ H ₇ C, - H. -, 6 13 , 35 ⁸ B 41 1.18 ^C 4 ^H 9 ^C 6 ^H 13 , 32 ³ B 40.5 - 1:19, ^C 6 ^H 13 6 13 , 36.5 • 38.5 48) Isio C ₃ H ₇ O ^C 6 ^H 13 ..40 44.5

Continued table

Verb. R ¹ 0 R ² K .5 V 3 ³ B 26 , 50 N I 2 I 1.21 ^C 4 ^H 9 1 ^C 6 ^H 13 .35 ♦ 44 • 50 · o ~ * e 1.22 C ₅ H ₁ 0 C ₆ H ₁₃ , 37 , 46 49. - " 1.23 ^C 6 ^H 1 ₅ ^{0 C} 6 ^H 13 , 34 , 45 53 1.24 C ₇ H ₁ 9 0 C ₆ H ₁₃ ♦ 45 , 50.5 55 1.25 C ₉ H ₁ Br T Γ ¹ TJ , 48   52.5 56.5. 1.26 NO ₂ O 1 Jl ^C 6 ^H 13 , 56 C 39) - - ♦ 1o27 CN 0 ^C 6 ^H 13 • 56 - - - 1.28 C ₄ H _{9 3} ^C 6 ^H 13 , 47 -. - 40.5) 1.29 C ₆ H ₁ 'C ₇ H ₁₅ , 49 .5 , 59.5 - -, Io 30 CN 3 0 C ₇ H ₁₅ 0 37 , 62 "-. 1.31 ^C 6 ^H 1 0 C ₇ H ₁₅ , 54 - - C 52) 1:32 C ₂ H ₅ C ₈ H ₁₇ , 38 , 60 ~ - 1:33 C ₄ H ₉ ^C 8 ^H 17 , 55 - «. C 55) 1o34 C ₅ H ₁ ^C 8 ^H 17 , 43 , 62 - - _# 1:35 br ° ^C 8 ^H 17 , 38 , 60 - -. 1 * 36 CN C ₈ H ₁₇ 0 48 (44.5) 1:37 4 ^C 8 ^H 17 , 60 -R -. - C 51) table O R ⁴ 3 R ⁵ K N- Verb. C ₃ H ₇ C ₄ H ₉ O 2VV ^C 6 ^H 1 ^C 4 ^H 9 ^G , 44

Table 5 _R 1

Verb. R ¹ R ³ KS S ₁₃ NI

jd

, .IC ₆ H ₁ -JO C ₄ H ₉ O _β 136 (.124) ·. 166 - - ..

3.2 CN C.HqO ο 121 - -. ' - - r-202.

3.3 CN ^C 6 ^H 13 ο 83 - - - -. 152.

Example 3:

Process for the etherification of 2- / ~ 4-hydroxy-phenyl-7-5-alkyl-1,3-dioxanes

1. 0.1 mol of 2 - / "~ 4-hydroxy-phenylJ7" ™ 5-alkyl-1,3-dioxane is dissolved in 50 ml of abs. Dissolved tetrahydrofuran and treated with 0.12 mol of sodium. After stirring for 2 hours, 0.12 mole of corresponding alkyl bromide is added and the. Reaction mixture heated for 4 hours at reflux. Thereafter, the solvent is distilled off on a rotary evaporator, the reaction product was taken up in 100 ml of ether and the etherisohe phase washed twice with 100 ml'Wasser. The mixture is then dried over Na 2 SO 4, the solvent is distilled off and the residue is recrystallized from methanol (Table 6).

2 ", 0.1 mol of 2 ~ _l / f4-hydroxy - ^phen3''lJ7: -5 - alkyl - 1 _y 3 ~ dioxane is dissolved in Yiienig benzene and added to a suspension of 0.23 g (0, 1 g-atom) sodium in 100 ml abs. Given toluene. After three hours of heating to 80 ⁰ C is cooled to room temperature and O _y ii mol of alkyl bromide added then heated for 4 hours at 80 ⁰ C, and after cooling, the reaction mixture washed with water, dried over Na ₉ S0 _A , the solvent distilled off and the reaction product crystallized from methanol (Table 6).

- 8th

0.1 mol of 2- ^ ~ 4-hydroxy-phenyl_7'-5-alkyl-1,3-dioxane are added with stirring to the solution of 0.23 g (0.1 g-atom) of sodium in .100 ml Section. Ethanol. "Thereafter, 0, 1 mol of alkyl bromide are added and the Ansätζ heated for 4 hours at reflux. After distilling off the solvent, the residue is taken up in ether, washed, dried over Na ₂ SO ^, the ether was distilled off and the reaction product was recrystallized from methanol (Table 6).

10 Table 6

λγω - ,, - κ r> ~ yield n.Variant K _o

Verb. R · ^m 1 2 3 (5 &) ^S A

1 .13! ir MlLI ΓΙ ^C 4 ^H 9 4 95 83 85 , 44  - ~ * A * 40). 1 Η .24 ^C 6 ^H 13 5 93 - 71 * 44 (. 22). 56 ·. 1 • HU 6 96 75 78 , 45 50.5. 55 Example 4:

Process for the esterification of ^ - / ^ - 5-subst. -1,3-dioxanes and 2- / ~ 4-3ubs. ~ Phenyl__7-5 - hydroxy-

1,3-dioxanes.

1. The sodium salt of 0.1 mol of 2 ~ _/ ~ 4-hydroxy-phenyl_7 ~ 5 ~ subst.-1,3-dioxanes (prepared according to Example 3) is dissolved in 50 ml of abs. Tetrahydrofuran, ether, benzene or toluene with stirring with 0.15 mol of corresponding acid chloride, the reaction was allowed to stand overnight, the solvent was distilled off, the residue taken up in ether, washed with Na ₂ SO, dried and recrystallized from methanol. The yield is 90 - 95 ί of theory.

- 9 ~

_ Q -

2. 0.1 mol of 2 -l-4-hydroxy-phenyl_7-5-subst.-1,3-dioxane or, 0.1 mol of 2 - / "" 4-SUbSt-phenyl _f _7-5 - hyar oxy ~ 1,3-dioxanes are added in 15 ml abs. Dissolved pyridine and slowly added with cooling and stirring 0.11 mol of corresponding acid chloride. The reaction mixture is allowed to stand overnight, the solvent is then distilled off and the Rüokstand worked up as described under 1.. The yield is 90 <f o of theory.

table

R-COO-

Verb,

1._38 C ₄ H ₉

i ^ io C ₆ H ₁₃ .

1:41

1.5 1.42 C ₅ H ₁₁ O-

Itu

C ₇ H ₁ 5 • 34 S _B 68 , 42 C ₇ H ₁ 5 * 27 q -7. r \ A , 148.5 C ₇ H ₁ 5 .1 80th 5 ~ -. , 193 C ₇ H ₁ 5 .1 85 _ _ , 174 η tr ^U 7 1 VJL 03 _ - _ _ CH ₁ 5 13 S _A 166o5

C ₇ H

7

.129 .S _A 182.5 ;

table

Verb, R 1.45

R *

C ₆ H ₁

-ζ VoOC-R ^

S N

, 143 - -. 159 ·

• lad. "-" - "· -" - ₀

- ίο -

Example 5:

Synthesis procedure for 5-alkyl-2- / ~ 4- (ß-cyanethyloxy) -phenyl YES, 3-dioxanes and 5- / ^r "ß-cyanoethyl oxy_7-2- / ~ 4-UBS s t. ~ 1.3 phenyl__7 -dioxane

To a solution of 0.1 mole of 5-Älkyl ~ 2 / f "4-hydroxyphenyl _i> J7" -1,3-dioxane and 0.1 mole of 2- / ^r 4r-substituted phenylJ / ^P -5 -hydroxy-1,3-dioxane are added at 35 to 40 ⁰ C 300 mg of sodium methylate and °, 12 moles of acrylonitrile. The reaction mixture is stirred for 6 hours at room temperature and then extracted with ether.

The ethereal phase is washed, dried with potash and the solvent distilled off. The residue is crystallized from methanol. The yield is $ 54- $ 80 of theory.

Claims (1)

Invention sans pruch Process for the preparation of crystalline-liquid 2,5-disubstituted derivatives of 1,3-dioxane of general formula X) - \ in which or X χ = R or X * R ¹ '~ and Y * IT, and Y = R- ¹ and Y «R ³ . mean such as ₅ C _n H _{2n + 1} OCOO; C _n ^ ) N; CN; NO ₂ ; F; Cl; Br; NC-CH = CH; NC-CH ₂ -CH ₂ ; NC-CH ₂ ^{4 4} J OCOOR ⁴ ; OCO- (Q) -R ¹ ; OCO- (h) -R ⁴ ; 5 ^C1 ' ^Br ' * ^CN ' with η can be «1» to 10,
geketinz-.e lehnet thereby., That alkanals j substituted benzaldehyde © "or« acetals with glycerol or .2-3ubstituted Propandiolen- (1 _? 3) in organic solvents in the presence of an organic cata- sector are reacted-which optionally still esterified or etherified