DE19515371A1 - New spiro:oxazine photochromic cpds. - Google Patents

Abstract

Spirooxazines of formula (I) are new: (where, R1-R4 = H, halogen, G, OG, -NG2 or -OT; R5-R7 = G; R8 = H, -NG2 or -1-piperidyl; R9, R10 = H, halogen, G or -OG; G = 1-6C alkyl, 5-7C cycloalkyl, phenyl, naphthyl or benzyl; T = polycyclic and/or methyl-substd. aliphatic ring system (e.g. adamantane or pref. a bi- or tricycloheptane such as norbornane (2.2.1), pinane (3.3.1), norcarane (4.1.0) or tricyclene), an aza system (e.g. 1-azabicyclo(2.2.2)octane or 3-azabicyclo(3.2.2) nonane), or one or more of (CH2)n-CO-G, -(CH2)n-O-(CH2)m-CH3, -(CH2)n-O-(CH2)n-O-(CH2)m-CH3, (CH2)n-CO-O(CH2)mn-G, or (CH2)n-O-CO-(CH2)mn-G; n = 1-4; and m = 0-3. At least one of R1-R4, R9 or R10 = -O-phenyl, -O-benzyl or -OT).

Description

The invention relates to photochromic spirooxazine Compounds and especially on specially-substituted Indolinospironaphthoxazine.

Spirooxazines exhibit photochromic compared to others high long-term stability. Well for this reason too, no other class is photo Chromic compounds in the past 25 years has been processed like the indolinospironaphthoxa zine. Last but not least, this is expressed in a large one  Number of patent applications, some of which are connections themselves, some of their applications.

The basic body of the spirooxazine compounds is be already described in U.S. Patents 3,578,602 and 3,562,172 ben; in these publications only Ver described bonds that only substituents on Have indoline subsystem.

In the applications EP 245.020 A1, EP 134.633 A1, US-PS 4,215,010 and US Pat. No. 4,342,668 are then also substituents specified on other subsystems. Furthermore are benzo-fused or aza-substituted indoline or naphthalene subsystems have been proposed; here to EP 141.407 A1, in which the substituent Quinoline is described, or on EP 232.295 A1 in which the substituent described isoquinoline ben is.

This class provides dyes that are under light color deep red to teal. Along with Dyes from the class of naphthopyrans, the yellow up to orange-red shades can do the whole thing visible spectrum are covered. To achieve cosmetically appealing neutral colors, such as gray or brown, from photo colored with these dyes chrome plastic eyeglass lenses is therefore one Mix of representatives of these two classes chatting.

According to the invention it has been recognized that a decision important role for the properties of photochromic glasses glasses and in particular their long-term stability Behavior in high vacuum during the anti-reflective treatment plays.  

Above all, there is a low tendency to migrate of the photochromic dyes even at high temperatures to promote.

The invention has for its object photochromic Specify spirooxazine compounds, even at high Temperatures and / or in vacuum a low Migra tend to have.

An inventive solution to this problem is in Claim 1 specified. Further training of the Erfin are subject of the subclaims.

The invention is based on the knowledge that it Introduction of special substituents is possible or the photochromic dyes better in the polymer too fix, d. H. drastically reduce the tendency to migrate put.

This happens with polycyclic ring systems, such as for example Adamantan or Campher, through the steri hindrance due to the bulky substituents Substituents that have groups similar to the poly mer, however, by the interaction with the polymer.

The invention is described in more detail below:

The compounds according to the invention are spirooxazine Connections with the general structure  

mean here

• - R₁, R₂, R₃ and R₄ independently of one another Substituent from the series: -H, halogen, -G, -OG, -NG₂ or -OT;
• - R₅, R₆ and R₇ independently of one another a sub stituent from the series: -G;
• - R₈ is a substituent from the series: -H, -NG₂ or -1-piperidyl;
• - R₉, R₁₀ independently of one another a substituent from the series: - H, halogen, -G or -OG and

G is a C₁-C₆-alkyl, C₅-C₇-cycloalkyl, phenyl, naphthyl or benzyl,
wherein at least one of the radicals R _1-4 or R₉ or R₁₀ -O-phenyl, -O-benzyl or -OT, and
T either a polycyclic and / or methyl-substituted aliphatic ring system (adamantane and preferably a bi- or tricycloheptane such as norbornane [2.2.1], pinane [3.3.1], norcarane [4.1.0] or tricyclene) or an aza system such as 1- Azabicyclo [2.2.2] octane and 3-Azabicyclo [3.2.2] nonane or one of the following groups:

In a preferred further education specified in claim 2, two adjacent radicals are connected by a -O- (CH₂) _1-3 -O bridge. Furthermore, the radicals R₆ and R₇ together with the indoline carbon atom can also form a C₅-C₇ cycloalkane ring (claim 3).

Bulky residues such as the polycyclic ring mentioned systems also offer the advantage that 2.6- Alkoxynaphthalenes known dimerization under light to prevent exposure. This occurs due to the very high dye concentrations in the surface dye exercise in plastic materials. Even minor ones Migration leads to the long period of use of the glasses to a noticeable loss of photochromic performance. This is also due to the training according to the invention increases the service life.

Examples of the polycyclic aliphatic ring system are Adamantan, Camphor, Norbornan etc.

Possible synthetic routes are described below:  

Synthetic route A

The compounds of the invention are synthesized in in a manner known per se, starting from the 2.6- or 2.7- Dihydroxynaphthalene. A hydroxy group is created by Ben coylation esterified (protected), the second subsequently with an alkyl halide, preferably iodide or bromide etherified. The ester then becomes free again Hydroxy group saponified alkaline. After nitrosation in 1-position to the free hydroxy group is by reaction with an active methylene indole base (substituted Fischer's base) the photochromic compound as Naphthoxazine synthesized. In this step too at the same time, if desired, the substituent R₈ via the Condensing agent introduced.

Below is the synthesis using an example exem Plarely described. The different fiction moderate connections are in the same way by the Obtain use of the corresponding alkyl halides:

1. Synthesis of 6-benzoyloxy-2-naphthol

75 g of commercially available 2,6-dihydroxynaphthalene are in a 2 l Three-neck flask in 450 ml freshly distilled off over Na Dioxane dissolved with stirring and heating. Then 150 ml of freshly distilled benzoyl chloride and then 33 ml of freshly distilled pyridine added. Under strong Stirring will result in the mixture separating into two phases NEN tried to reflux for 4 h.

The hot mixture is poured into 10 liters of cold water and continued stirring. The unusual mono and diesters  are filtered off, washed with hot water and ge dries. By boiling in 500 ml of ethanol for 5 minutes most of the monoester was brought into solution. The solution is filtered hot, the remaining residue Diester washed out with hot alcohol. By diluting the alcoholic solution with 10 times the amount of 2% -NaHCO₃- Solution, the monoester is precipitated. This will start filtered, washed and dried at 120 ° C (12 min). Repeated recrystallization from toluene gives the product (81 g) in colorless leaves: M.p .: 190-191 ° C.

2. Reaction with phenacyl bromide (halide)

25.5 g of the benzoic acid ester from 1 are triturated with 19.9 g Phenacyl bromide and 14.0 g of anhydrous potassium carbonate as intimately as possible. This mixture is dry in 150 ml Suspended acetone and boiled under reflux for 3 hours. The solution is filtered. After removing the acetone from the Filtrate is taken up in CH₂Cl₂, unreacted Naphthol is poured out of the filtrate with dilute NaOH telt. The organ. Phase is dried, filtered and the Solvent removed. Aceto formed as a by-product phenon remains in solution and in the next synthesis step is separated in this way.

3. Cleavage of the ester

The ester is boiled for 3 minutes in aqueous alcoholic KOH split, the naphthol is replaced by An acidify the alkaline solution with dilute acetic acid precipitated, filtered off. After washing with dil. NaHCO₃-  Solution to remove adhering benzoic acid residues the product dried. It will be without further cleaning used.

4. Nitrosation of the ester

42 g of finely ground 6-phenacyloxy-2-naphthol with ice cooling in 400 ml of glacial acetic acid and 80 ml of water suspended. 11 g NaNO₂ in an addition, 0.5 white tere grams added after 10 min. The mixture is 2 h stirred and then the precipitated mass filtered. This is diluted with aqueous dilute acetic acid, then washed out with water. The light ocher colored Product is used without further cleaning.

5. Implementation with the Fischer base

23.1 g of nitroso product from 4. are mixed with 15 g of 1,3,3- Trimethyl-2-methylene-5-methoxy-indoline and with 10 Drop of piperidine dissolved in 250 ml of ethanol and 4 h cooked under reflux. The amount will be half Concentrated volume in vacuum and allowed to cool. The failed crystal masses are sucked off and columned with ethanol on Al₂O₃. Which is under UV light strongly turquoise-blue fractions are collected. After removing the ethanol, pour something over it Acetone and leaves covered. After 4 days the precipitated crystals are filtered off and in ethanol washed. The product, a fine yellow powder, NMR analysis showed that spiro (5-methoxyindoline 2,3'-8'-phenacyloxy-naphth [2,1-b] oxazine) become.  

If R₈ is not to be H but an amine function, this remainder is transferred to the condensing agent in one One-pot reaction introduced. The 2- up to 3 times the molar amount of secondary amine, for example wise piperidine, dibutylamine, dicyclohexylamine or the like instead of the above quantities. For the introduction of the Rest of O-benzyl, O-phenyl or O-T at R₁₀ instead of R₉ is made of 2,7- instead of 2,6-dihydroxy-naphthalene went out.

Synthetic route B

The introduction of the rest of the invention in the In dolin part usually takes place before the actual one Indole synthesis.

Which may seem easier at first glance method of per-alkylation of the commercially available 5-hydroxyindoles and etherification of the free hydroxy group with the residues according to the invention results only very much poor yields.

The use of ether gives better results phenylamines and their implementation.

In all cases, the indoline base is in the form of its Indolenium salt (methyl iodide) used, since most of the time existing ester functions under the conditions of Formation of the free methylene base using strong alkali be hydrolyzed.

The following example is intended only as an example demonstrate:  

93 g of commercially available phenoxyphenylamine is dissolved in 1 liter of toluene dissolved and dry HCl gas passed through. The first The precipitate is filtered off and white with acetone washed. 74 g (0.3 mol) of this hydrochloride with 62 g (0.3 mol) phenoxyphenylamine and (0.3 mol) 29.5 g (0.3 mol) acetoin finely ground, to melt brought and stirred for 30 minutes in an oil bath (140 ° C). The healed melt is in a rough glass or porcelain shell tilted and allowed to solidify.

After crushing, it is pulverized and 2 h in 3 l Stirred 12% hydrochloric acid. The precipitate sucked off is washed with 2% HCl, dried and in warm Dissolved ethanol (60 ° C). Fall in the freezer overnight (-28 ° C) crystals. These are sucked off, that The filtrate was concentrated to 1/4. Thereby more crystals fall out. The combined yellow to ocher Crystal masses are recrystallized twice from ethanol. The NMR analysis of the white, silvery needles the product as

2,3-dimethyl-5-phenoxy-indole.

45 g of this compound are in 100 ml of ethanol with 45 g Methyl iodide added, reversed for 4 h in an autoclave at 105 ° C puts. After cooling overnight, the mixture is on Rotavap the solvent and excess alkylation withdrawn medium. The dark oil is poured into 80 ml KOH (31 g KOH added to 80 ml H₂O), heated to 75 ° C, 30 min stirred, allowed to cool and poured out with ether telt. After drying with Na₂SO₄ and filtering the ether removed from the filtrate. The fractional HV Distillation gives several fractions, of which the middle, in addition to 3,3-dimethyl-2-methylene-5-phenoxy  indole still 1,3,3-trimethyl-2-methylene-5-phenoxy-indole and contain 2,3,3-trimethyl-5-phenoxy-indolenine, be united.

66 g of this mixture (from 2 batches) are mixed with 50 g Methyl iodide dissolved in as little DMF as possible and 45 min cooked on a water bath. After the deduction of the release and Alkylating agent becomes the remaining tarry black Mass extracted in the extractor with toluene. The remaining one gray-brown crystal mass is converted from ethanol / water crystallized. The NMR analysis of the salt shows:

1,1,3,3-tetramethyl-2-methyl-5-phenoxy-indolenium (iodide).

The non-commercially available etherphenylamines are made Aminophenols and alkyl bromide (after acetylation of the Amino function) obtained analogously to synthesis route A2.

The conversion to photochromic also takes place Spiroindolino-naphthoxazine analogous to AS, but because of the use of the indolenium salt at least equimolar Amounts of condensing agent are required.

Of course, Ver bonds are generated, both in the indoline, as in Naphthoxazinteil corresponding ethers and / or Bear ester functions by in the aforementioned reaction analogous to A 5, the nitroso products obtained in A 4 be set.  

Table 1

With the inventive and the comparative compounds  According to known methods (DE 35 16 568 A1) surfaces colored zero glasses made of diethylene glycol bisallyl car bonat were subjected to normal cleaning and then in a high vacuum with a multiple layer for anti-reflective coating (DE 43 11 572 A1).

The glasses were left at room temperature for 42 hours and then a boiling test in 4% NaCl solution throw. The test was carried out for 2 minutes Glasses checked for layer detachments. The test was until the beginning of layer separation, but at most Repeated 12 times. The substances according to the invention showed significantly better behavior, which indicates the ver reduced migration of the photochromic dyes to the Surface can be traced, which leads to the detachment of evaporated anti-reflective layers leads.  

Table 2

Beginning of layer detachment in the xth test cycle: 20 glasses per test series

They are striking compared to the almost simultaneously  experiments with photochromic pyrans P 44 17 894.8 better results of those examined here Oxazine.

Claims (4)

1. Spirooxazine compounds with the general structure mean here

• - R₁, R₂, R₃ and R₄ independently of one another a substituent from the series: -H, halogen, -G, -OG, -NG₂ or -OT;
• - R₅, R₆ and R₇ independently of one another a sub-substituent from the series: -G;
• - R₈ is a substituent from the series: -H, -NG₂ or -1-piperidyl;
• - R₉, R₁₀ independently of one another from the series: - H, halogen, -G or -OG and

G is a C₁-C₆-alkyl, C₅-C₇-cycloalkyl, phenyl, naphthyl or benzyl,
wherein at least one of the radicals R _1-4 or R₉ or R₁₀ -O-phenyl, -O-benzyl or -OT, and
T either a polycyclic and / or methyl-substituted aliphatic ring system (adamantane and preferably a bi- or tricycloheptane such as norbornane [2.2.1], pinane [3.3.1], norcarane [4.1.0] or tricyclene) or an aza system such as 1- Azabicyclo [2.2.2] octane and 3-Azabicyclo [3.2.2] nonane or one of the following groups: 2. Spirooxazine according to claim 1, characterized in that two adjacent residues are also connected by a -O- (CH₂) _1-3 -O bridge. 3. spirooxazine according to claim 1 or 2, characterized in that R₆ and R₇ together with the indoline carbon atom also has a C₅-C₇ cycloalkane ring form.