DD153690A1 - PROCESS FOR THE PREPARATION OF PHOTOCHROMENE 1,4-2H-OXAZINES AND SPIROPHENANTHRO-1,4-2H-OXAZINES - Google Patents

Abstract

It has been found that novel 1,4-2H-oxazines and spirophenanthro-1,4-2H-oxazines of the general formulas, which because of their structure have photochromic properties with high spectral changes and high reversibility, can be prepared by a process characterized by that phenanthrenequinone monoxime and naphthoquinone monoxime or derivatives thereof with 1,1'-diarylethylenes or Alkylidenheterocyclen or their precursors, the quaternary salts of the general structures in which R deep 1, R deep 2, R deep 3, hydrogen, chlorine, bromine, alkyl, cyano , Nitro, dialkylamino, alkoxy, carbalkoxy, carboxylic acid groups, Rtief4 hydrogen, alkyl, aryl group R -N (alkyl) deep 2; -N (Ctief 2 H deep 4 OH) (C deep 2 H deep 4 CN); -N (C deep 2 H deep 4 OH) deep 2; -N (C deep 2 H deep 4 CN) deep 2 -N (CH deep 2) deep 4 O; -O-alkyl X - an alkylimino, arylimino or sulfur; Y is a dialkylmethylene group or sulfur-Z-iodide, perchlorate, p-toluenesulfonate, are reacted in a conventional manner in the presence of acidic or basic condensing agent. This process is characterized by a simple reaction route with high yields and small, easily removable by-products and is due to the variety of possibilities for the synthesis of many novel basic bodies, such as 14-2H-naphthoxazines, Indolinospirophenanthro-1.4-2H-oxazines, Benzthiazolino-1,4- 2H-oxazines and varied derivatives of these are applicable.

Description

Process for the preparation of photochromic 1,4-2H-oxazines and spirophenanthro-1,4-2H-oxazines

Field of application of the invention

The invention relates to a process for the preparation of photochromic 1,4-2H-oxazines and spirophenanthro-1,4-2H-oxazines, which may have the following general structures:

Compounds of these types possess photochromic properties due to the possibility of photoinduced reversible ring opening to form color rich azamerocyanines. they reversibly change their absorption spectrum on exposure. This change is possible both in crystalline form, in solution or in polymer embedding. These properties allow the use of such compounds as photochromic media for a variety of applications. Prerequisite for this is u. a. a sufficiently large wavelength difference between the activated and non-activated form, relatively high sensitivity, high seversibility, good Lichttransparenζ the non-activated form and high optical densities of the activated form. · ·

To be able to optimize all these requirements, the synthesis of a wide range of compounds with suitable substituents is necessary. This has been predominantly up to now

J. · ² 222988

In particular, a variety of derivatives have been synthesized by introducing substituents in the benzopyran moiety of the indolinospiropyran backbone to improve the required parameters Synthesis of substituted o-hydroxy aldehydes as starting materials is necessary, which mostly runs over many stages with partly low yields and often different formation of different isomers with difficult and time-consuming separation processes.

The preparation of the 1,4-2H-0xazines according to the invention and spirophenanthro-1,4-2H-oxazines according to the invention is carried out in good yields "from synthetically readily accessible phenanthrenequinone monoximes without large amounts of by-products or condensation by condensation with methylene bases Substituents are available and various alkylidene heterocycles can be used for condensation, a very wide range of substituted 1,4-2H-0xazinen or Spirophenanthro-1 ^ -Pü-oxazinen different body accessible.

The 1 _o 4-2H-0: xazines according to the invention and spirophenanthro-1,4-2H-oxazines are generally photochromic and are characterized in addition to large spectral changes between the activated and non-activated form, relatively high sensitivity of the actinic form, simple synthetic routes with good Yields and minor by-products in particular by a remarkably high .Reversibilität with good, by Substituenten- and media choice largely variable properties. ί 30

3 2229 88

Characteristic of the known technical solutions

For the preparation of 1,4-2H-0xä.zinen the following reaction pathway is described in the literature:

(SnCl ₂ }

This reaction proceeds only in poor yields, is accompanied by side reactions and is not particularly suitable for the synthesis of photochemically substituted in the 2-position photochromic 1.4-2H-0xazines, which can form color deep Azamerocyanine by light-induced ring opening. The synthesis of the hitherto unknown 1 4-2H phenanthroxazines according to the invention can not be realized in this way.

because the necessary starting materials (especially those in on

9.10-position by OH- and NOp-groups substituted phenanthrene compounds) hitherto unknown · For the synthesis of Spirophenanthro-1.4-2H-oxazines according to the invention there is hitherto no synthetic route, since this class of compounds has not yet been described.

Object of the invention

The aim of the invention is to facilitate the synthesis of novel 1,4-2H-oxazines and spirophenanthro-1,4-2H-oxazines in a wide variety in a simple way. The 1,4-2H-0xazines and spirophenanthro-1,4-2H-oxazines according to the invention should preferably have photochromic properties with a large wavelength difference between the activated and non-activated form, high sensitivity and high reversibility.

22 2 9

Ί Presentation of the essence of the invention

The known syntheses for the preparation of 1,4-2H-oxazines are not suitable for the preparation of such representatives, which due to their structure may undergo a light-induced, thermally reversible ring-opening-ring reaction to form color-rich azamerocyanines.

It has been found that per se known o-quinone monocycles of phenanthrene and naphthalene and their derivatives of the formulas 1 and 2, 10th

N = O

in which R 1, R ₂ 7 / oxygen, chlorine, bromine, alkyl, cyano, nitro

Dialkylamino, alkoxy, carbalkoxy, carboxylic acid

groups for the preparation of 1,4-2H-oxazines with known 1,1'-diarylethylenes of the general formula

in the

E _{4 is} hydrogen, an alkyl or aryl group R -N (alkyl) ₂ ; -N (C ₂ H ₄ OH) (C ₂ H ₄ CN); -N (C ₂ H -N (CH ₂ O ₄ O; -O-alkyl

and for the synthesis of spirophenanthro-1,4-2H-oxazines the

Compounds of the formula 1 and 2 with per se known Alkyiidenheterocycien of the general formula.

2229

= CHR

or the salts of the general formula

in which

R is hydrogen, chlorine, bromine, alkyl, nitro, alkoxy,

Carbalkoxy, carboxylic acid groups R ₂ ,. Hydrogen, a long or short chain alkyl or

aryl

Y is a dialky! Methylene group or sulfur X is an alkylimino (alkyl-IT =), aryl iniino group (aryl-E =)

or sulfur Z ~ iodide, perchlorate or p-toluenesulfonate

mean,

to novel photochromic 1,4-2H-oxazines, preferably 2,2 * -bis (p-dialkylaminophenyl) -phenanthro-1,4-2H-oxazines and 2,2'-bis (p-dialkylamino-phenyl) -naphtho-1,4-2H-oxazines of the formulas

22 2 9 88

or to novel spirophenanthro-1,4-2H-oxazines, preferably indolinospirophenanthro-1,4-2H-oxazines, in particular those of the formula

^R 2 R ^rx 3

or BeDzthiazolinospirophenanthr0-1.4-2H-OXaZiDeD, in particular. 10 special ones of the formulas

"2 ^IX 3;

or Bendithiolinospirophenanthro-1,4 ~ 2E-oxazines, especially those of the formula

20

implements.

The reactions proceed according to the following scheme:

  '

- 1.4-2H-0xazines

30 35

222988

- Spirophenanthro-1,4-2H-oxazines

The condensation is conveniently carried out in at the Beaktionstemper atur en liquid solvents, -As alcohols or aromatic hydrocarbons, optionally in the presence of basic or acidic condensing agent such as piperidine, pyridine, glacial acetic acid or Lewis acids such as AlCLa, ZnCIg with for condensation reactions of the present A _r t amounts known per se and carried out under customary condensation conditions. Conveniently, the condensation at temperatures in the range of 50 is - 120 ⁰ C, if appropriate, carried out under änaeroben conditions. The oxazines and spirooxazines which precipitate out of the solution or crystallize after appropriate workup are yellow to brown compounds, which are purified in the usual way preferably by recrystallization from ethanol. They give in the known organic solvents, depending on the polarity, colorless to pale yellow or blue to green-blue solutions, depending on whether the ring-closed or the colored Azamerocyaninform represents the thermodynamically stable isomers. The colorless to pale yellow solutions or solid solutions, if the oxazines or spirooxazines according to the invention were embedded in a polymer matrix, discolor on irradiation with UV light or by tincrease or upon contact with acidic carrier substances such as silica gel , reversibly intense

8 22 2 9 88

blue to greenish blue. The previously color-deep solutions can be reversibly decolorized with visible light of suitable wavelengths.

embodiments

The following examples are intended to illustrate the synthesis of novel photochromic !? 1.4-2H - 0xasine and spirophenanthro-1.4-2H-oxasine without limiting it in any way.

example 1

0.01 mole of phenanthrenequinone monoxime and 0.01 mole of 1,1'-bis (p-dimethylaminophenyl) ethylene are dissolved in 50 ml of anhydrous ethanol. It is added to a few drops of glacial acetic acid and boiled under nitrogen atmosphere for 8 hours on Eückfluß. It is then treated with 1 N NaOH and extracted several times with ether. The combined ether extracts are dried over Ra ₂ SO ₄ , then the solvent is evaporated. The remaining precipitate is recrystallized from ethanol. This gives yellow-brown crystals, mp 126 ⁰ C, which dissolve in the usual organic solvents (yield: 55 % of theory ).

Elementänalysen:

> 5 o

81.4% 81.2%

Mass spectrum: 471 m / e (mole peak)

UV / VIS spectrum: colorless form: λ, = 260 nm (ethanol),

EcUv

Color form: L, = 610 nm (ethanol)

H Έ 6.15 % 8,92 1 6.2 % 8.74 j I theor. I practice .

22 29 88

Example 2

1> 75 S lO ^ trimethyl ^ -methylene-indoline (Pischer base) and 2.85 g of 2.7-dinitrophenanthrenequinone monoxime are boiled in about 50 ml of anhydrous ethanol for 2 days under baking flow. After cooling, the resulting reaction product is washed with a little anhydrous ethanol, dissolved in benzene and shaken with 1 11 ITaOH. The solid obtained from 3ensen is i'O'-trimethylindolino-spiro-ö.ii-dinitrophenanthro-1.4-2H-OXaZIn

 10

Mass spectrum (peak matching):

Molepeak:. ,

Exp .: 468, 1449

calc .: 468, 1434 (for C ₂₆ H ₂₀ N ₄ O ₅ )

Example 3

1,2-Dimethylbenzthiazoliumoodid and phenanthrenequinone monoxime are refluxed in molar ratio in anhydrous ethanol with the addition of a few drops of piperidine for 24 hours. The reaction product is worked up as in Example 2. The resulting reaction product is 1'-methylbenzothiazolinospiro-phenantliroxazine (yield: 60 % of theory ). In Benzen and other organic solvents it shows inverse photochromism from blue to colorless.

Example 4

DitMoliumperchlorat, prepared by well-known method of ethylenedithiol and acetyl chloride, is refluxed with phenanthrenequinone monoxime in an equimolar ratio in nitromethane in the presence of piperidine for 8 hours. The work-up is carried out analogously to Example 2.

With SO% yield Dithiolinospirophenanthro-1.4-2H-oxazine is obtained (mp 290 ° C). The compound was confirmed by elemental analysis and mass spectrometry. A solution in toluene turns blue when exposed to UV light.

Claims (1)

22 2 9 88 invention claim 1. A process for the preparation of photothromed 1.4-2H-0xazinen and spirophenanthro-1.4-2H ~ oxazines characterized in that phenanthrenequinone monoxime or naphthoquinone monoxime and derivatives thereof with 1,1'-bis (p-dialkylaminophenyl) ethylene, 1,1'-bis (p-alkoxyphenyl ) ethylenes or Alkylidenheteroeyclen bzv /. their precursors, the quaternary salts of Ar Ar in a manner known per se in the presence of an acidic or basic catalyst, such as glacial acetic acid, piperidine, pyridine or Lewis acids, such as AlCln, ZnCl ₂ in amounts known per se and under customary conditions to give the novel 1,4-2H-oxazines. ¹ O or spirophenanthro-1,4-2H-oxazines of the following general structures, / 25 in which Ar Hydrogen, alkyl, nitro, dialkylamino, alkoxy, carbalkoxy or cyano groups,. Hydrogen, an alkyl or aryl group, a benzene nucleus substituted in the p-position by the following groups: ₂₂₄ ; -N (CH ₂ ) ₄ O; -O-alkyl 2229 88 1 X is an alkylimino or arylimino group (All-cyl-N or Aryl-lO or sulfur, Y is a dialkylmethylene group or sulfur mean, \
5 are condensed.