CA1335503C - Spiro-oxazine compound - Google Patents

Abstract

A spiro-oxazine compound represented by the following general formula (A) or (A') is a photochromic compound having an excellent fatigue resistance to repetition of color development and decolorization and an abundance of hues:

(A) or

Description

`

DESCRIPTION
.

TITLE OF THE INVENTION
Novel Spiro-Oxazine Compound TECHNICAL FIELD
The present invention relates to a spiro-oxazine compound. More particularly, the present invention relates to a photochromic compound valuable as a printing material, an optical recording material, a recording material, a clothing material, a decorating material and the like.
BACKGROUND ART
A spiropyran compound can be mentioned as a typical photochromic compound, and many photochromic spiropyran compounds are known [G. H. Brown, "Photochromism", Wiley Interscience, New York ~1971)].
Spiropyran compounds, however, have a problem of poor fatigue resistance at the repetition of coloration and decoloration.
A spiro-oxazine compound is known as a photochromic compound having an improved fatigue resistance. For Pxample, Japanese Unexamined Patent Publication No.
62-205185 discloses the following compound:

However, In the conventional spiro-oxazine compounds, however, the hue of the chromophoric seed is limited to violet-to-blue, and thus they have a low selection of hues.
DISCLOSURE OF THE INVENTION
The present invention is intended to overcome the above-mentioned defects of the conventional technique, and an object of the present invention is to provide a photochro-mic compound having an excellent fatigue resistance upon a repetit'on of coloration and decoloration and an abundance of hues.
In accordance with one embodiment of the present invention there is provided a spiro oxazine compound represented by the following formula (A) or (A'):

or ( ~ C\ i~ ~ i / (A') ~"
R2k whereir. the ~ ring is a ring selected from the group consisting of a 5-membered ring having one nitrogen atom, a 5-membered ring having one nitrogen atom and connected to a benzene ring or naphth~lene ring and a 6-membered ring having one nitrogen atom, with the proviso that the nitrogen atom in the ~ ring is bonded to an organic group R and is expressed as > N-R wherein R is a subs ituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 133S50~

20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms and an aryl group having 6 to 19 carbon atoms; the ~ ring is a ben-zene r-ng or a naphthalene ring; X is selected from the group consisting of 0, S, Se and N-R1 wherein R1 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an ara kyl group having 7 to 20 carbon atoms, an aryl group having 6 to 19 carbon atoms and an acyl group having 2 to 20 carbon atoms; R2 and R3 are a substituent selected from the group consisting of a hydrogen atom, a hydroxyl group, an amino group having 0 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 14 carbon atoms, a halogen group, a cyano group, a carboxyl group, a nitro group, an acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a carbamoyl group having 2 to 20 carbon atoms, a carbamoyloxy group having 2 to 20 carbon atoms, and a sulfonic acid group, with the proviso that R2 is not a hydrogen atom, and R3 is not a nitro group; and k is a integer of from 0 to 2. .
Ir.accordance with another embodiment of the present inven-tion there is provided a spiro-oxazine compound represented by the following formula (B) or (B'):

P` m -- 3a -or R m R ~ .

whereir R is a substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms and an aryl group having 6 to 19 carbon atoms; X is select~.d from the group consisting of O, S, Se and N-R1 wherein Rl is selected from the group consisting of a hydrogen atom, an alkyl croup having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 19 carbon atoms and an acyl group having 2 to 20 carbon atoms; R2 and R3 are a substituent select~d from the group consisting of a hydrogen atom, a hydroxyl group, an amino group having 0 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 14 carbon atoms, a halogen group, a cyano group, a carboxyl group, a nitro group, an acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a carbamoyl group having 2 to 20 carbon atoms, a carba-moylox~I group having 2 to 20 carbon atoms, and a sulfonic acid .cj - 3b -group, with the proviso that R2 is not a hydrogen atom, and R3 is not a r.itro group; and k is a integer of from 0 to 2; R4 and R5 indeper.dently stand for a substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms and an aryl group having 6 to 19 carbon atoms, or R4 and R5 together form a cycloalkyl group having 3 to 10 carbon atoms with the carbon atoms Lt the 3'-position, R6 and R7 stand for a substituent select~d from the group consisting of a hydroxyl group, an amino group having 0 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, an ary~oxy group having 6 to 14 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 14 carbon atoms, a halogen group, a cyano group, a carboxyl group, a nitro group, an acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a carbamoyl group having 1 to 20 carbon atoms, a carbamoyloxy group having 2 to 20 carbon atoms and a sulfonic acid group, and ~ and m stand for an integer of from 0 to 4.
Ir.yet another embodiment of the present invention there is provid~d a spiro-oxazine compound represented by the following formul~ (C) or (C'):

~7~ (C) r C

1335~03 or S , --~ (C ) m wherein R is a substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon ~.toms and an aryl group having 6 to 19 carbon atoms; X is selected from the group consisting of O, S, Se and N-R1 wherein R1 is s~lected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 19 carbon atoms and an acyl group having 2 to 20 carbon atoms; R2 and R3 are a substituent selected from the group consisting of a hydrogen atom, a hydroxyl group, an amino group having 0 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to lS carbon atoms, an aryl group having 6 to 14 carbon atoms, a halogen group, a cyano group, a carboxyl group, a nitro group, an acyl group having 2 to 20 c-.rbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a carbamoyl group having 2 to 20 carbon atoms, a carba-moyloxy group having 2 to 20 carbon atoms, and a sulfonic acid group, with the proviso that R2 is not a hydrogen atom, and R3 is not a ritro group; and k is a integer of from 0 to 2; R4 and Rs indeperdently are selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to ;,,. rc, 20 carhon atoms and an aryl group having 6 to 19 carbon atoms, or R4 ~nd R5 together form a cycloalkyl group having 3 to 10 carbon atoms with the carbon atoms at the 3'-position, R6 and R7 are se_ected from the group consisting of a hydroxyl group, an amino group having 0 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 lo carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralky_ group having 7 to 15 carbon atoms, an aryl group having 6 to 14 carbon atoms, a halogen group, a cyano group, a carboxyl group, a nitro group, an acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a carbamoyl group having 1 to 20 carbon atoms, a carbamoyloxy group having 2 to 20 carbon atoms and a sulfonic acid group, and ~ and m are an integer of from 0 to 4, R8 is selected from the group consis ing of a hydroxyl group, an amino group having 0 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkeny:L group having 2 to 20 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 14 carbon atoms, a halogen group, a cyano group, a carboxyl group, a nitro group, an acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a carbamoyl group having 1 to 20 carbon atoms, a carbamoyloxy group having 2 to ~0 carbon atoms and a sulfonic acid group, and n is an intege- of from 0 to 2.
In accordance with a further embodiment of the present invention there is provided a spiro-oxazine compound represented by the following formula (D) or (D'):

-13~S503 - 3e -R8n R4R5R3 ~, , R7 ~ ~ (0) k ~7 wherein R is a substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon ~toms and an ar~l group having 6 to lg carbon atoms; X is selected from the group consisting of 0, S, Se and N-R1 wherein R1 is s~lected from the group consisting of a hydrogen atom, an alkyl g-oup having 1 to 20 carbon atoms, an alkenyl group having 2 to 2C carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 19 carbon atoms and an acyl group h.ving 2 to 20 carbon atoms; R2 and R3 are a substituent selected from the group consisting of a hydrogen atom, a hydroxyl group, an amino group having 0 to 20 carbon atoms, an alkoxy group h~ving 1 to 20 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 14 carbon atoms, a halogen group, a cyano group, a carboxyl group, a nitro group, an acyl group having 2 to 20 c-.rbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a carbamoyl group having 2 to 20 carbon atoms, a carba-C

- 3f -moyloxy group having 2 to 20 carbon atoms, and a sulfonic acid group, with the proviso that R2 is not a hydrogen atom, and R3 is not a nitro group; and k is a integer of from 0 to 2; R4 and R5 independently are selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms and an aryl group having 6 to 19 carbon atoms, or R4 ~nd R5 together form a cycloalkyl group having 3 to 10 carbon atoms with the carbon atoms at the 3'-position, R6 and R7 are se:ected from the group consisting of a hydroxyl group, an amino group having 0 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralky: group having 7 to 15 carbon atoms, an aryl group having 6 to 14 carbon atoms, a halogen group, a cyano group, a carboxyl group, a nitro group, an acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a carbamoyl group having 1 to 20 carbon atoms, a carbamoyloxy group having 2 to 20 carbon atoms and a sulfonic acid group, and and m are an int~ger of from 0 to 4, R8 is selected from the group consis-ting of a hydroxyl group, an amino group having 0 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, an alk~l group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 14 carbon atoms, a haloger group, a cyano group, a carboxyl group, a nitro group, an acy: group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a carbamoyl group having 1 to 20 carbon atoms, a carbamoyloxy group having 2 to 20 carbon atoms and a ~ulfonic acid group, and n is an integer of from 0 to 2.
In accordance with another embodiment of the present C' - 3g -invention there is provided a spiro-oxazine compound represented by the following formula (E) or (E'):

Rl r ~ (E) .. ..
~ k or lS ~ ~ ~ 6 ~2 wherein R is a substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon ~toms and an aryl group having 6 to 19 carbon atoms; X is selected from the group consisting of 0, S, Se and N-R1 wherein R1 is selected from the group consisting of a hydrogen atom, an alkyl g~oup having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 19 carbon atoms and an acyl group having 2 to 20 carbon atoms; RZ and R3 are a substituent selected from the group consisting of a hydrogen atom, a hydroxyl group, an amino group having 0 to 20 carbon atoms, an alkoxy group h-.ving 1 to 20 carbon atoms, an aralkoxy group having 7 to r~

- 3h -15 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an acy:oxy group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 14 carbon atoms, a halogen group, a cyano group, a carboxyl group, a nitro group, an acyl group having 2 to 20 c~rbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a carbamoyl group having 2 to 20 carbon atoms, a carba-moyloxy group having 2 to 20 carbon atoms, and a sulfonic acid group, with the proviso that R2 is not a hydrogen atom, and R3 is not a r.itro group; and k is a integer of from 0 to 2; R4 and R5 indeperdently are selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms and an aryl group having 6 to 19 carbon atoms, or R4 -.nd R5 together form a cycloalkyl group having 3 to 10 carbon atoms with the carbon atoms at the 3'-position, R6 and R7 are selected from the group consisting of a hydroxyl group, an amino roup having 0 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 14 carbon atoms, a halogen group, a cyano group, a carboxyl group, a nitro group, an acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a carbamoyl group having 1 to 20 carbon atoms, a carbamoyloxy group having 2 to 20 carbon atoms and a sulfonic acid group, and ~ and m are an integer of from 0 to 4, R9, R10, R11, R12, R13 and R14 are selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms and an aryl group having 6 to 19 carbon atoms.
In accordance with a still further embodiment of the present invent-on there is provided a spiro-oxazine compound represented C

- 3i -by the Collowing formula (F) or (F'):

~ F) or lS R m~

R R2 (F') wherein R is a substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms and an aryl group having 6 to 19 carbon atoms; X is select~.d from the group consisting of O, S, Se and N-R1 wherein R1 is ~elected from the group consisting of a hydrogen atom, an alkyl ~roup having 1 to 20 carbon atoms, an alkenyl group having 2 to ~0 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 19 carbon atoms and an acyl group having 2 to 20 carbon atoms; R2 and R3 are a substituent selected from the group consisting of a hydrogen atom, a hydroxyl group, an amino group having 0 to 20 carbon atoms, an alkoxy group laving 1 to 20 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, an alkyl group havin 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbor atoms, an aralkyl group having 7 to 15 carbon atoms, an rC j 1~3S503 - 3j -aryl group having 6 to 14 carbon atoms, a halogen group, a cyano group, a carboxyl group, a nitro group, an acyl group having 2 to 20 c~rbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a carbamoyl group having 2 to 20 carbon atoms, a carba-moyloxy group having 2 to 20 carbon atoms, and a sulfonic acid group, with the proviso that R2 is not a hydrogen atom, and R3 is not a ritro group; and k is a integer of from 0 to 2; R4 and R5 independently are selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms and an aryl group having 6 to 19 carbon atoms, or R4 ~nd R5 together form a cycloalkyl group having 3 to 10 carbon atoms with the carbon atoms at the 3'-position, R6 and R7 stand for a substituent selected from the group consisting of a hydroxyl group, an amino group having 0 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, an alkyl croup having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 14 carbon atoms, a halogen group, a cyano group, a carboxyl group, a nitro group, an acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 2~ carbon atoms, a carbamoyl group having 1 to 20 carbon atoms, a carbamoyloxy group having 2 to 20 carbon atoms and a sulfon c acid group, and ~ and m stand for an integer of from 0 to 4, R15 is selected from the group consisting of a hydroxyl group, an amino group having 0 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkoxy group having 7 to 15 car~on atoms, an aryloxy group having 6 to 14 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 14 carbon atoms, a halogen group, a cyano group, a carboxyl group, a nitro group, an alkoxycarbonyl group C

133~50~

- 3k -having 2 to 20 carbon atoms, a carbamoyl group having l to 20 carbon atoms, a carbamoyloxy group having 1 to 20 carbon atoms and a sulfonic acid group, and t is an integer of from O to 2.
BEST MODE OF CARRYING OUT THE INVENTION
Ir the compound of the present invention represented by the general formula (A) or (A'), the ~ ring is a 5-membered or 6-membered ring having one nitrogen atom, or a 5-membered ring having one nitrogen atom and connected to a benzene ring or naphth~lene ring. As specific examples, there can be mentioned a pyrrolidine ring, a pyrrole ring, a piperidine ring, a tetrahydropyridine ring, a dihydropyridine ring, an indoline ring, ~nd a benzindoline ring.
Tke nitrogen atom contained in the ~ ring is bonded to an organic group R as expressed as >N-R.

~ ~CI

~ ~ 4 ~ 13~5503 As specific examples of the substituent R0, there can be mentioned linear alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl and octadecyl groups, branched alkyl groups having 3 to 20 carbon ~toms, such as tert-butyl and 2-methylpentyl groups, cycloalkyl groups having 3 to 10 carbon atoms, such as cyclohexyl, norbornyl and adamantyl groups, alkenyl groups having 2 to 20 carbon atoms, such as vinyl, ~llyl, hexenyl, 1,3-butadienyl and isopropenyl groups, ~ralkyl groups having 7 to 20 carbon atoms, such as ~enzyl, phenethyl and (2-naphthyl)methyl groups, and ~ryl groups having 6 to lg carbon atoms, such as phenyl -.nd 2-naphthyl groups. R0 may be substituted. A~
specific examples of the substituent for R0, there can be mentioned a hydroxyl group, amino groups such as amino, dibenzylamino and (2-methacryloxyethyl)amino groups, alkoxy groups such as methoxy, ethoxy and propoxy groups, acyloxy groups such as acetoxy, benzoyloxy, acryloxy and methacryloxy groups, alkyl groups such as methyl, ethyl, trifluoromethyl and butyl groups, ara~l groups such as benzyl and 4-(2,3-epoxy-propyl)phenethyl groups, aryl groups such as phenyl and styryl groups, halogen groups such as fluoro and chloro groups, a cyano group, a carboxyl group, a nitro group, an acetyl group, acyl groups such as a methacryl group, alkoxycarbonyl groups such as ethoxycarbonyl and 3,~-epoxybutyloxycarbonyl groups, carbamoyl groups such as carbamoyl, N-phenylcarbamoyl and N-(2-methacryloxy)ethylcarbamoyl groups, carbamoyloxy groups such as an ~N-(acryloxy)propylcarbamoyl]oxy group, and sulfonic acid groups such as a sulfonic acid group and metal salts thereof (for example, sodium and lithium salts).
The ~ ring, which is included in the general formula (A) or (A') as well as the ~ ring, is a benzene ring or a naphthalene ring.
Other constituents included in the general formula 1335~03 (A) or (A') will now be described.
X is one member selected from the group consisting of O, S, Se and N-Rl, in which Rl stands for one member ~elected from the group consisting of a hydrogen atom, ~n alkyl group having 1 to 20 carbon atoms, an alkenyl croup having 2 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 9 carbon atoms and an acyl group having 2 to 20 carbon atoms. R1 may be substituted. As specific examples of the alkyl, alkenyl, aralkyl and aryl groups as R1, nclusive of substituents contained in R1, there can be mentioned those exemplified above with respect to R0, ~nd as the acyl group, there can be mentioned an acetyl group and a methacryl group.
In order to obtain a compound having an excellent -epetition durability and having a plurality of ~bsorption wavelengths of the chromophoric seed, X is preferably O. Furthermore, to obtain a chromophoric ~eed of a bright red hue,X is preferably N-Rl.
As specific examples of R2 and R3, there can be nentioned a hydroxyl group, substituted and unsub-~tituted amino groups such as amino, dimethylamino, dibenzylamino and (2-methacryloxyethyl)amino groups, ~lkoxy groups having 1 to 20 carbon atoms, such as ]nethoxy, ethoxy, propoxy and butoxy groups, aralkoxy groups having 7 to 15 carbon atoms, such as benzyloxy ~nd phenethyloxy groups, aryloxy groups having 6 to 14 carbon atoms, such as phenoxy and naphthyloxy groups, Acyloxy groups having 2 to 20 carbon atoms, such as -benzoyloxy, acryloxy and methacryloxy groups, alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, propyl, butyl, tert-butyl, glycidyl and octadecyl groups, alkenyl groups having 2 to 20 carbon atoms, such -.s vinyl, allyl, isopropenyl, 1,3-butadienyl and 9,12-octadecadienyl groups, aralkyl groups having 7 to 15 carbon atoms, such as benzyl, phenetyl and naphthyl-methyl groups, aryl groups having 6 to 14 carbon atoms, B~

~ - 6 - 1335S03 uch as phenyl and naphthyl groups, halogen groups such ~s chloro, fluoro and bromo groups, a cyano group, a c~rhoxyl group, a nitro group (not included in R3), acyl groups having 2 to 20 carbon atoms, such as acetyl, nethacryl and acryl groups, alkoxycArhonyl groups having 2 to 20 carbon atoms, such as ethoxycarbonyl and .,4-epoxybutyloxycarbonyl groups, unsubstituted and ~ubstituted carbamoyl groups such as carbamoyl, r-phenylcarbamoyl and N-(2-methacryloxy)ethylcarbamoyl groups, carbamoyloxy groups such as N-(3-acryloxy)propylcarbamoyl]oxy and [N-(methacryl-oxy)propylcarbamoyl]oxy groups, and sulfonic acid y-OUp8 'not included in R3) such as a sulfonic acid group and netal salts thereof (for example, sodium and lithium ~alts). Furthermore, a hydrogen atom is included in R .
Note, k is an integer of from 0 to 2, and where k ~s 2, two R2 groups may be the same or different.
As specific examples of the spiro-oxazine compound of the present invention represented by the general 'ormula (A) or (A'), there can be mentioned the 'ollowing compounds.
(a) Spiro-oxazine compounds represented by the 'ollowing general formula (B) or (B'):
R7 ~ R6 or R7 ~ ` ~ \ ' ~\ X~

~O
R k wherein R0, R2, R3, X and k are as d~fined in the general formula (A) or (A'), R4 and R5 independently stand for a substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms and an aryl group having 6 to 19 carbon atoms, or R4 and R5 together form a cycloalXyl group having 3 to 10 carbon atoms with the carbon atom at the 3-position, R6 and R7 stand for a substituent selected from the group consisting of a hydroxyl group, an amino group having 0 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 14 carbon atoms, a halogen group, a cyano group, a carboxyl group, a nitro group, an acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a carbamoyl group having 1 to 20 carbon atoms, a carbamoyloxy group having 2 to 20 carbon atoms, and a sulfonic acid group, and Q and m stand for an integer of from 0 to 4.
(b) Spiro-oxazine compounds represented by the following general formula (C) or (C'):

. . .

r~an ~ (c ) wherein R , R , R , X and k are as defined in the general formula (A) or (A'), R , R , R , R , Q and m are as defined in the general formula (B) or (B'), R8 stands for a substituent selected from the group consisting of a hydroxyl group, an amino group having 0 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 14 carbon atoms, a halogen atom, a cyano group, a carboxyl group, a nitro group, an acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a carbamoyl group having 1 to 20 carbon atoms, a carbamoyloxy group having 2 to 20 carbon atoms,and a sulfonic acid group, and n is an integer of from 0 to 2.
~c) Spiro-oxazine compounds represented by the following general formula (D) or (D'):

m or ~, R7 ~ - R6 wherein RO, R2, R3, X and k are as defined in the general formula (A) or (A'), R4, R5, R6, R7, ~ and m are as defined in the general formula (B) 1~ or (B'), and R8 and n are as defined in the general formula (C) or (C').
(d) Spiro-oxazine compounds represented by the following general formula (E) or (E'):

R12 ~ R6 or RR12 ~ ~ R6 R2k wherein RO, R2, R3, X and k are as defined in the general formula (A) or (A'), R4, R5, R6 and ~ are as defined in the general formula (B) or (B'), and 9 10 Rll Rl 2 R13 and R14 stand for one member selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms and an aryl group having 6 to 19 carbon atoms.
(e) Spiro-oxazine compounds represented by the general formula (F) or (F'):

_ - lO - ~ 13635503 3 ~

R7 ~ 15 or R7 ~ 15 R2k (F~ ) wherein R0, R2, R3, X and k are as defined in the general formula (A) or (A'), R4, R5, R6, R7, and m are as defined in the general formula (B) or (B'), R15 stands for a substituent selected from the group consisting of a hydroxyl group, an amino group having 0 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 14 carbon atoms, a halogen atom, a cyano group, a carboxyl group, a nitro group, an alkoxycarbonyl group having 2 to 20 carbon atoms, a carbamoyl group having 1 to 20 carbon atoms, a carbamoyloxy group having 2 to 20 carbon atoms, and a sulfonic acid group, and t is an integer of from 0 to 2.
In the spiro-oxazine compounds represented by the above-mentioned general formulae (B), (B'), (C), (C'), (D) and (D'), as specific examples of R4 and R5 which are independent from each other, there can be mentioned linear alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl and octadecyl groups, branched alkyl groups having 3 to 20 carbon atoms, such as a 2-methyl-pentyl group, cycloalkyl groups having 3 to 10 carbon atoms, such as a cyclohexyl group, aralkyl groups having 7 to 20 carbon atoms, such as benzyl and phenethyl groups and aryl groups having 6 to 19 carbon atoms, such as a phenyl group, and as specific examples of the group formed by combined R4 and R5 together with the carbon at the 3-position, there can be mentioned cycloalkyl groups having 3 to 10 carbon atoms, such as cyclohexyl, norbornyl and adamantyl groups.
R4 and R5 may be substituted. As the substituent for R4 and R5, there can be mentioned those exemplified above as the substituent for R0.
R6, R7 and R8 are as defined in the general formula (A) or (A') with respect to R2. ~, m and n are as defined above, and if they are 2 or more, two or more of corresponding R6, R7 or R8 groups may be the same or different.
In the spiro-oxazine compounds represented by the above-mentioned general formula (E) or (E'), R0, R2, R3, R4, R5, R6, X, k and I are as defined in the above-mentioned general formulae (A), (A'), (B), (B'), (C), ( ), (D) and (D'), and R~, R10, Rll R12 R13 d 14 are selected from the group consisting of a hydrogen - atom and the same alkyl, aralkyl and aryl groups as exemplified above with respect to R2 in the general formula (A) or (A'). All of these groups may be the same or different.
In the spiro-oxazine compounds represented by the ` general formula (F) or (F'), groups other than R15 are as mentioned in the other general formulae, and R15 is sélected from group~ exemplified above with respect to R0 in the general formula (A) or (A'). If t is 2, two R15 groups may be the same or different.
As is apparent from the foregoing description, the ....

spiro-oxazine compound of the present invention is characterized in that the spiro-oxazine compound comprises not only the above-mentioned ~ ring but also an oxazine ring, a benzene ring, a heterocyclic 5-membered ring and the ~ ring. Especially, a compound in which the benzene ring, heterocyclic 5-membered ring and ~ ring are consecutively by connected, R3 is a hydrogen atom and X is O, S or Se, has absorptions in both of the short wavelength region (less than 550 nm) and long wavelength region (more than 600 nm) of the visible ray region, and even a compound develop ng a green color can be obtained. Furthermore, if R has a substituent other than hydrogen or X is N-Rl, a compound developing a red color can be obtained. Accordingly, the spiro-oxazine compound of the present invention has an abundance of chromophoric seed. Moreover, the spiro-oxazine compound o the present invention has an excellent fatigue resistance to the repetition of coloration and ~ecoloration.
The general formulae (A) and (A') in the present invention are isomeric to each other, and an appropriate isomer is selected according to the intended object in view of the kinds of substituents and the desired photochromic characteristics.
The compound of the present invention represented by the formula (A) or (A') is prepared, for example, according to the following processes.
According to the first process, a methylene compound represented by the following general formula (I): _ ~ ~ C=CHR (I) is reacted with-a nitroso compound represented by the following general formula (II) or (II'):

HO ¦ R k ) or ~ /~ , NO
to prepare a compound represented by the formula (A) or (A').
According to the second process, a compound 0 represented by the following general formula (III):
~ ~ C- CH2R3 (III) is reacted with-a quaternarizing agent R0-Y (Y stands for an anionic leavin~ grou~), a basic ~ stance and a compound represented by the general formula (II) or (II') in an optional order to obtain a compound represented by the formula (A) or (A').
According to the third process, a reaction product between a compound represented by the formula (I) and nitrous acid is reacted with an amino compound represented by the following general formula (IV) or (IV'):

HO I /R k ~ ` ~ ~`~ (IV) or ~ ~, (IV') to prepare a compound represented by the formula (A) or (A').
According to the fourth process, a reaction product between a compound represented by the formula (III) and nitrous acid is reacted with a quaternarizing agent R0-Y, a basic substance and a compound represented by the general formula (IV) or (IV') in an optional order to prepare a compound represented by the formula (A) or (A').
According to the fifth process, a reaction product ~1 , . .

between a compound represented by the following general formula (V):
C-CH2R3 (V) \ROY-and nitrous acid is reacted with a basic substance and a compound represented by the general formula (IV) or (IV') in an optional order to prepare a compound represented by the formula (A) or (A').
As the purification method in the preparation process, preferably recrystallization using various solvents, column chromatography separation using a silica column or the like, solvent extraction and active carbon treatment are adopted.
The spiro-oxazine compound of the present invention is preferably used in combination with an optically transparent resin. As the resin, there can be mentioned, for example, a diethylene glycol bis-allyl-carbonate polymer, a (meth)acrylic polymer, a copolymer thereof, a cellulose, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, a polyester resin, polycarbonate, polystyrene, a copolymer thereof, an ! epoxy resin, a (halogenated) bisphenol A di(meth)-acrylate polymer, a copolymer thereof, a (halogenated) bisphenol A urethane-modified di(meth)acrylate polymer, a copolymer thereof, a nylon resin and polyurethane.
If the spiro-oxazine compound of the present invention has an alkenyl group, that is, a polymerizable functional group such as a methacryloxy group or a vinyl group, by copolymerization of this spiro-oxazine compound with other polymerizable compound such as an acrylic monomer, a styrene type monomer or a vinyl acetate type monomer, the spiro-oxazine compound can be integrated with a polymer resin of the other polymerizable compound. If the spiro-oxazine compound is thus integrated by the copolymerization, a preferred photochromic material having an excellent durability of ,~
r" ., ~ .,,1 . .

- 15 - 133~503 he spiro-oxazine compound can be obt~ine~.
Compounds of the general formulae (A) through (F) ~nd (A') through (F') having polymerizable functional groups at R0, R2, R6, R7 and R15 are preferable from the viewpoint of the durability. Compounds having a ~olymerizable functional group at R0, which is introduced through a methylene chain having at least 3 ¢arbon atoms, are especially preferred. A methacryloxy ~roup is especially preferred as the polymerizable 'unctional group, because the radical polymerization is æasily accomplished and decomposition is prevented during the polymerization.
If the compound of the present invention has a polymerizable functional group, the compound can be used in the form of not only a copolymer as mentioned above ~ut also a homopolymer.
The photochromic compound of the present invention can be preferably used as an optical element having photochromic characteristics in the form of a combina-ion with a resin, a polymer of the compound or acombination of this polymer with other resin. As the optical element, there can be mentioned sunglass lens, -ki goggles and protective glass lens. Furthermore, the photochromic compound of the present invention can be preferably used for curt~ining, clothing, automobile ~indows such as a front glass or sun roof, toys, toilet ~rticles and writing tools.
A8 the method for combining the photochromic compound of the present invention, various methods can be adopted, for example, a dyeing method, a casting ~ethod and a polymer solution-coating method. Instead of the polymer solution-coating method, a method can be ~dopted in which an emulsion is formed and the emulsion is coated by screen printing. Moreover, various 2rinting methods, for example, a gravure printing method, can be adopted. As the coating method, various coating methods can be adopted, such as a dip coating ~ - 16 -1335~03 method, a spin coating method and a roli coating method.
In many cases, the chromophoric seed of the compound of the present invention has at least two absorption peaks, and therefore, the compound of the present invention is valuable as a material for a rewritable optical disk.
The amount of the compound of the present invention to be combined with the resin should be determined according to the ob~ect and the application method, but from the viewpoint of visual sensitivity, preferably the amount of the compound of the present invention is O.Ol to 20% by weight based on the resin.
To improve the repetition durability of the photochromic compound of the present invention, pref-erably oxygen and water are intercepted when thecompound of the present invention is used. Furthermore, known additives can be used to further improve the durability. For example, there can be used a singlet oxygen quencher represented by a nickel salt, an antioxidant represented by a hindered amine or a polymer thereof and an ultraviolet absorber having no influence on the photochromic characteristics.
The present invention will now be described in detail with reference to the following examples that by no means limit the scope of the invention.
Example l (l) Synthesis of l-nitroso-2-hydroxydibenzofuran In lO0 g of pyridine was dissolved lO g of 2-hydroxydibenzofuran, and the solution was cooled to 0C. Then, 60 g of a 20~ aqueous solution of sodium nitrite was added to the above solution and lO0 g of a 30~ aqueous solution of sulfuric acid was added dropwise to the mixture while stirring for lO minutes. After the dropwise addition, the mixture was stirred at 0C for l hour and then filtered. The recovered solid was washed with water and dried to obtain ll g of a red crystal of l-nitroso-2-hydroxydibenzofuran.

t~

(2) Results of analysis Elementary analysis values:
Found Value (%) Calculated Value (%) C67.7 67.7 H3.2 3.3 N6.3 6.6 NMR (protons other than OH): 6.7 ppm (d, lH), 7.4 ppm (t, lH), 7.5 ppm (t, lH), 7.6 ppm (d, lH), 7.7 ppm (d, lH), 8.3 ppm (d, lH) (3) Synthesiæ of spiro-oxazine of following 'ormula (G):

'' " 1 ` ~ (G) In 100 ml of absolute ethanol were dissolved 10 g of 1,3,3-trimethyl-2-methylene-indoline and 10 g of ~-nitroso-2-hydroxydibenzofuran, and reaction was ~arried out at the reflux temperature for 1 hour. After he reaction, the reaction mixture was concentrated and -ub~ected to column chromatography separation using -ilica gel as the supporting carrier and methylene ~hloride as the developing solvent. Distillation of lethylene chloride gave a pink solid, and recrystal-Lization from methanol gave a white crystal of the -piro-oxazine of the formula (G).

(4) Results of analysis Elementary analysis values:
Found Value (~) Calculated Value (%) C 78.8 78.3 H 5.8 5.4 N 7.2 7.6 NNR: 1.4 ppm (6H), 2.8 ppm (3H), 6.6-8.5 ppm -_ 18 - 1335503 (llH) Melting point: 158C

(5) Application A coating solution was prepared by dissolving ~.1 g of the spiro-oxazine of the formula (G) in 100 g of a 10~ solution of polyvinyl butyral in butanol, and he coating solution was coated on two glass sheets.
~he coated glass sheets were dried and piled so that the =esin-coated surfaces confronted each other, and the ~iled glass sheets were heated.
When the so-prepared photochromic laminated ~lass was irradiated with ultraviolet rays, the _aminated glass became green. If the light was removed ~nd the laminated glass was allowed to stand in the dark, the laminated glass became colorless again. When he laminated glass was irradiated with light for 20 hours in a fadeometer and the light resistance was ~xamined, it was found that the photochromic character-~stics were the same as those before the placement in he fade meter, and it was confirmed that the fatigue -esistance was excellent. When the absorption charac-eristics at the time of coloration in methanol were ~xamined, it was found that absorption peaks ~max ~ppeared at 460 nm and 632 nm.
ExamPle 2 (1) Synthesis of spiro-oxazine of following -ormula (S):
CH CH
C1 , ~ N~
Cl I ?' (s) A white cry~tal of the spiro-oxazine of the Cormula (S) was obtained in the same manner as described _n Example 1 except that 1,3,3-trimethyl-2-methylene-5,6-dichloroindoline was used instead of 1,3,3-trimethyl-2-methyleneindoline.
(2) Results of analysis Elementary analysis values:
Found Value (%~ Calculated Value (%) C 66.1 65.9 H 3.8 4.1 N 6.5 6.4 Melting point: 204 - 205C
NMR: 1.5 ppm (6H), 2.8 ppm (3H), 6.4-8.4 ppm (9H) (3) Application A laminated glass was prepared in the same manner as described in Example 1 by using the so-obtained compound. When the laminated glass was irradiated with ultraviolet rays, the laminated glass became green, and if the light was ~ ved and the laminated glass was allowed to stand in the dark, the 20 1 ~mi n~ted glass became colorless again. When the laminated glass was irradiated with light for 20 hours in a fadeometer and the light resistance was ex~mined, it was found that the photochromic characteristics were the same as those before the placement in the fadeometer 25 and the light resistance was excellent.
ExamPle 3 (1) Synthesis of spiro-oxazine of formula (H) ~ ~ ~ ~ (H) H3C ~ CH3 H3C ~ CH3 In 100 ml of benzene were dissolved 10 g of 2,3,3-trimethylindolenine and 15 g of 2,3,4,5,6-penta-methylbenzyl chloride, and the solution was refluxed for 2 hours. Then, the temperature of the reaction liquid was lowered to about 50C, and 3 g of triethylamine and 10 g of 1-nitroso-2-hydroxydibenzofuran were added to the reaction liquid. Reaction was carried out at the reflux temperature for 1 hour. Then, the purification was carried out in the same manner as described in Example 1 to obtain a white crystal of the spiro-oxazine of the formula (G).
(2) Results of analysis Elementary analysis values:
Found Value ~%) Calculated Value (~) C81.9 81.7 H6.8 6.6 N5.2 5.4 NNR: 1.4 ppm ~6H), 2.2 ppm (15H), 4.3 ppm ~ (2H), 6.4-8.5 ppm (llH) (3) Application A laminated glass was prepared in the same manner as described in Example 1 by using the 80-prepared compound. When the absorption characteristics of the laminated glass at the time of coloration were examined, it was found that the absorption peaks ~max appeared at 460 nm and 632 nm.
Examples 4 throuqh 11 (1) The following compounds having substituents at the positions a through g were prepared in the same manner as described in Example 3.

- 21 - 13355~3 O ` ~

g ~ c f ~ d e The compound of Example 4 had Cl at each of he positions a, b, c and e.
The compound of Example 5 had F at each of the 20sitions c, d, e, f and g.
The compound of Example 6 had OCH3 at each of he positions a and c and N02 at the position e.
The compound of Example 7 had a methacryloxy qroup at the position a.
The compound of Example 8 had a methoxy group dt the position a and a vinyl group at the position e.
The compound of Example 9 had H at each of the ~ositions a through g.
The compound of Exmple 10 had Cl at each of he postions c and e.
The compound of Example 11 had CH3 at the 20sition d.
(2) Results of analysis Elementary analysis values:

~ - 22 - 1335503 C (%) H (%) N (%) Example 4 62.2 3.5 4.7 (61.9) (3.4) (4.8) Example 5 67.5 3.9 5.0 (67.4) (3.6) (5.2) Example 6 70.3 5.2 7.6 (69.9) (4.9) (7.7) Example 7 77.1 5.2 5.3 (77.3) (5.3) (5.3) Example 8 79.0 5.3 5.7 (79.2) (5.6) (5.6) Example 9 81.1 5.3 6.3 (81-1) (5 4) (6.3) Example 1070.2 4.0 5.5 (70.2) (4.3) (5.5) Example 1181.0 5.8 6.0 (81-2) (5 7) (6.1) Each value is a found value but each of the ~arenthesized values is a calculated value.
NMR:
Example 9: 1.4 ppm (6H), 4.4 ppm (4H), 6.3-8.4 ppm (16H) Example 10: 1.4 ppm (6H), 4.5 ppm (2H), 6.3-8.4 ppm (14H) Example 11: 1.4 ppm (6H), 2.3 ppm (3H), 4.5 ppm (2H), 6.2-8.5 ppm Melting point:
Example 9: 157 - 158C
Example 10: 150C
3~ (3) Application Laminated glasses were prepared in the æame nanner as described in Example 1 by using the compounds of Examples 4 through 6. Each of the laminated glasses ~ecame green under irradiation with ultraviolet rays.
In 20 g of toluene were dissolved 1 g of the compound of Example 7 and 10 g of n-butyl methacrylate, - - 23 - 133550~
~nd solution polymerization was carried out by using ~zobisisobutyronitrile as the polymerization initiator.
When the polymer solution was coated on a slide glass, a ransparent coating film was obtained. When the glass sheet was irradiated with ultraviolet rays, the glass ~heet became green, and when the light was removed and -he glass sheet was allowed to stand in the dark, the glass sheet became colorless again.
A glass sheet was similarly prepared by using he compound of Example 8, and the glass sheet became green under irradiation with ultraviolet rays.
A coating solution formed by dissolving 0.1 g of the compound of Example 9 in a 10% solution of an ~crylic polymer in toluene was coated on two glass ~heets. The glass sheets were dried and piled so that he resin-coated surfaces confronted each other, and the _aminate then heated.
When the so-prepared photochromic laminated glass was irradiated with ultraviolet rays, the aminated glass became green, and when the light was -emoved and the laminated glass was allowed to stand in he dark, the laminated glass became colorless again.
~hen the laminated glass was irradiated with light for 20 hours in a fadeometer and the light resistance was ~xamined, it was found that the photochromic character-~stics were the same as those before the placement in he fadeometer and the light resistance was excellent.
~hen the absorption characteristics at the time of coloration were examined, it was found that the ~b80rption peaks ~max appeared at 486 nm and 632 nm.
A laminated glass was prepared in the same anner as described above by using the compound of ~xample 10, and when the absorption characteristics at he time of coloration were examined, it was found that he absorption peaks ~max appeared at 486 nm and 628 nm.
A coating solution comprising 0.1 g of the compound of Example 11, 0.03 g of a hindered amine type light stabilizer (*LA-57 supplied by Adeca-Argus), 0.04 g of a hindered amine type light stabilizer (*LA-77 supplied by Adeca-Argus), 0!02 g of a hindered phenol type antioxidant (*AO-60 supplied by Adeca-Argus), 0.01 g S of di(2-ethylhexyl) adipate as a plasticizer, 0.1 g of dimethyl diphenate and 100 g of a 10% solution of polyvinyl butyral in butanol was coated on two glass sheets. The coated glass sheets were dried and piled so that the resin-coated surfaces confronted each other, and the laminate then heated. When the so-prepared photochromic laminated glass was irradiated with ultraviolet rays, the laminated glass became green, and when the light was removed and the laminated glass was allowed to stand in the dark, the laminated glass became colorless again. When the laminated glass was irra-diated with light for 20 hours in a fadeometer and the light resistance was examined, it was found that the light resistance was good.
Example 12 (1) Synthesis of spiro-oxazine of following formula (I):

N <,~ ~ ' ~ (I) (iH2)6 o C -C=CH2 To a solution comprising 15 g of 1-(6-hydroxy-hexyl)-2,3,3-trimethylindolenium iodide, 10 g of triethylamine and 100 ml of methylene chloride was added dropwise 15 g of methacryloyl chloride. After the dropwise addition, the mixture was stirred for 1 hour.
Then, 100 ml of water was added to the mixture, and the C

*Trade mark mixture was extracted with methylene chloride. The methylene chloride layer was concentrated to obtain 11 g of 1-(6-methacryloxy)hexyl-2-methylene-3,3-dimethyl-indoline. The reaction was carried out in the same manner as described in Example 1 except that the so-obtained compound was used instead of 1,3,3-trimethyl-2-methylene-indoline, whereby a yellow liqu1d of the spiro-oxazine of the formula (I) was obtained.
(2) Results of analysis Elementary analysis values:
Found Value (~j Calculated Value (%) C75.8 75.9 H- 6.4 6.5 N5.4 5.4 IR: 1720 cm 1 NMR: 1.2-2.0 ppm (17H), 3.2 ppm (2H), 4.1 ppm (2H), 5.5 ppm (lH), 6-1 ppm (lH)~
6.6-8.5 ppm (llH) (3) Application In the same manner as described in Example 7, a coated glass sheet was prepared by using the spiro-oxazine of the formula (I). When the glass sheet was irradiated with ultraviolet rays, the glass sheet became green, and when the light was Le,l-oved and the glass sheet was allowed to stand in the dark, the glass sheet became colorless again. When the absorption character-istics at the time of coloration were Px~mined, it was found that the absorption peaks ~max appeared at 486 nm and 633 nm.
When the glass sheet was subjected to the durability test where the glass sheet was irradiated with light for 20 hours in a fadeometer, no substantial degradation was observed, and it was confirmed that the glass sheet had a good durability.
Example 13 . , - 26 - 133~03 (1) Synthesis of spiro-oxazine compound of formula (J) 3~ 3 Cl CONH

H3CO ~ OCH3 The above compound was synthesized in a manner -imilar to the manner adopted in Example 1.
(2) Results of analysis Elementary analysis values:
Found Value (%) Calculated Value (%) C 72.2 72.4 H 5.4 5.3 N 7.4 7.7 IRs 3380 cm 1, 3340 cm 1, 1710 cm 1, 1540 cm~l, 1250 cm~l, 1025 cm~
(3) Application The spiro-oxazine of the formula (J) was dissolved in methyl methacrylate at a concentration of ~.5% by weight, and cast polymerization was carried out by using azobisisobutyronitrile as the polymerization initiator to obtain a polymethyl methacrylate sheet in which the compound of the formula (J) was incorporated.
When the sheet was irradiated with ultraviolet -ays, the sheet became green, and when the light was -emoved and the sheet was allowed to stand in the dark, ,he sheet promptly became colorless again. When the ~bsorption characteristics at the time of coloration were examined, it was found that the absorption peaks ~max appeared at 490 nm and 706 nm. This sheet became green even at 50C under irradiation with ultraviolet rays, and the coloration-possible temperature was higher than 50C.
ExamPle 14 (1) Synthesis of 2,3,3-trimethylbenz(g)indolenine To 10 g of l-naphthylhydrazine hydrochloride ~nd 30 g of methyl isopropyl ketone was added dropwise 5 g of sulfuric acid, and reaction was carried-out at the reflux temperature for 2 hours. The reaction nixture was neutralized with a 20% aqueous solution of ~odium hydroxide and extracted with water/ether, and the ether layer was concentrated to obtain 8 g of 2,3,3-trimethylbenz(g)indolenine.
(2) Synthesis of 1,2,3,3-tetramethylbenz(g)-_ndolenium iodide A solution comprising 8 g of 2,3,3-tri-nethylbenz(g)indolenine and 25 g of methyl iodide was -eacted at the reflux temperature for 30 minutes. The ~ormed precipitate was recovered by filtration and washed with acetone to obtain 12 g of a white crystal.
(3) Synthesis of spiro-oxazine of following 'ormula (R):
3, 3 ~ ~ N ~ (K) A æolution of 12 g of 1,2,3,3-tetramethyl-~enz(g)indolenium iodide and 10 g of 1-nitroso-2-~ydroxydibenzofuran in 50 ml of isopropanol was heated o 50C, and 5 g of piperidine was added to the ~olution. Then, reaction was carried out at the reflux emperature for 1 hour. The reaction mixture was ~oncentrated and sub~ected to the column chromatography -eparation using silica gel as the supporting carrier ~nd toluene as the developing solvent. Distillation of ,he solvent gave a pink solid. When this solid was recrystallized from butanol, a light yellow crystal of the compound of the formula (K) was obtained.
(4) Results of analysis Elementary analysis values:
Found Value (%) Calculated Value (%) C 80.5 80.4 H 5.6 5.3 N 6.4 6.7 NMR: 1.4 ppm (6H), 3.4 ppm (3H), 6.4-8.7 ppm (13H) (5) Application A laminated glass was prepared in the same manner as described in Example 9 by using the compound of the formula (K). When the laminated glass was rradiated with ultraviolet rays, the laminated glass became green, and when the light was removed and the _aminated glass was allowed to stand in the dark, the _aminated glass became colorless again. When the aminated glass was irradiated with light for 20 hours _n a fadeometer and the light resistance was examined, it was found that the photochromic characteristics were he same as those before the placement in the fadeometer ~nd the fatigue resistance was excellent. When the ~bsorption characteristics at the time of coloration ~ere examined, it was found that the absorption peaks ~max appeared at 465 nm and 650 nm.
Examples 15 throuah 18 Compounds of the following formula having sub-~tituents at the positions a and b were synthesized in a ~anner similar to the manner adopted in Example 7:
CH CH

133S~03 The compound of Example 15 had -CH2 ~\
~t the position a.
The compound of Example 16 had -CH3 at the position and -CO2H at the position b.
The compound of Example 17 had -CH3 at the posi-ion a and -CH2OH at the position b.
The compound of Example 18 had \0/

~t the position a and 1l ICH3 -CH20C-C=CH2 ~t the position b.
(2) Re6ults of analysis Elementary analysis values:
C (%) H (%) N (%) Example 15 82.9 5.3 5.4 (82.7) (5.5) (5.5) Example 16 75.3 4.7 6.0 (75.3) (4.8) (6.1) Example 17 77.4 5.3 6.2 (77.7) (5.4) (6.3) Example 18 75.2 5.2 4.7 (75.3) (5.4) (5.0) Each value is a found value, but each of the 2arenthesized values i8 a calculated value.
Laminated glasses were prepared in the same manner as described in Example 9 by using the compounds of Examples 15 through 17. Each of the laminated glasses became green under irradiation with ultraviolet -ays.
A glass sheet was prepared in the same manner a8 described in Example 7 by using the compound of ~ 1335~03 Example 1~. The glass sheet became green under irradia-tion with ultraviolet rays.
Example 19 (1) Synthesis of 2,3,3-trimethylbenz(f)indolenine Reaction was carried out in the same manner as described in (1) of Example 1~ except that 2-naphthyl hydrazine hydrochloride was used instead of l-naphthyl-hydrazine hydrochloride (2) Synthesis of spiro-oxazine of following 1~ formula (L):
Br ¦ ~ o ~ (L) In 40 ml of ethanol were dissolved 6 g of the compound prepared in (1) above and 10 g of methyl tosylate, and reaction was carriedout at the re~lux temperature for 2 hours. The temperature of the reaction liquid was lowered to 50C, and 2 g of triethylamine and 10 g of 1-nitroso-2-hydroxy-8-bromodibenzofuran were added to the reaction liquid.
Reaction was carried out at the reflux temperature for 2 hours, and the subsequent procedures were the same as described in Example 1 and a light yellow crystal of the compound of the formula (L) was obtained.
(3) Results of analysis Elementary analysis values:
Found Value (%~ Calculated Value (%~
C 67.3 67.6 H 4.0 4.2 N 5.7 5.6 Example 20 (1) Synthesis of 4,4-dimethyl-5-oxohexane-nitrile ~. ~,o,., `- - 31 - 1335503 A mixture of 40 g of 3-methyl-2-butanone and , g of Triton B was heated to 35C, and 20 g of ~crylonitrile was added to the mixture over a period of hour. Then, the mixture was stirred for 18 hours, and hydrochloric acid was added to the mixture to make the nixture acidic and the mixture was extracted with ether.
(2) Synthesis of compound of following formula (VI):

CH2 C-CH3 (VI) O

A mixture of 50 g of 4,4-dimethyl-5-oxo-hexane-nitrile, 6 g of ethylene glycol, 30 ml of petroleum ether and 0.3 g of p-toluenesulfonic acid nonohydrate was reacted at the reflux temperature for ~0 hours, and the reaction liquid was concentrated.
(3) Synthesis of compound of following formula 'VII):

CH2 C-CH3 (VII) A solution of 20 g of the compound of the formula (VI) in 200 ml of ether was added dropwise to 20 g of lithium aluminum hydride and 300 ml of ether over a period of 30 minutes, and reaction was carried ~ut at the reflux temperature for 2 hours and the -eaction liquid was cooled. Water was added to the ~eaction liquid to decompose the excess of lithium ~luminum hydride. The reaction mixture was filtered, ~nd the filtrate was concentrated.
(4) Synthesis of 2,3,3-trimethyl-3,4,5,6-tetrahydropyridine To a solution of 20 g of the compound of the formula (VII) in 50 ml of ethanol was added 110 ml of lN
hydrochloric acid, and the mixture was heated and refluxed for 1 hour. Then, the reaction mixture was concentrated.
(5) Synthesis of 1,3,3-trimethyl-2-methylene-piperidine A mixture of 5 g of 2,3,3-trimethyl-3,4,5,6-etrahydropyridine and 12 g of methyl tosylate was-eacted at 100C for 4 hours. The reaction mixture was cooled and extracted with water/chloroform. Then, 2 g of ~odium hydroxide was added to the water layer and the mixture was stirred. The liquid was extracted with chloroform. The chloroform layer was concentrated to obtain a yellow liquid.
(6) Synthesis of spiro-oxazine of following .-ormula (M):

1 ~ ~ ~' (M) A milky white crystal of the compound of the formula (M) was prepared in the same manner as described in Example 1 except that 1,3,3-trimethyl-2-methylene-piperidine was used instead of 1,3,3-trimethyl-2-methylene-indoline.

(7) Results of Analysis Blementary analysis values:
Found Value (%) Calculated Value (%) C 75.5 75.5 H 6.6 6.6 N 8.4 8.4 Exam~le 21 ~ ~ 33 ~ 1335~03 (1) Synthesis of spiro-oxazine of following formula (N):

~ ~:` j n (N) CH20C-C=CH2 A white crystal of the spiro-oxazine of the formula (N) was prepared in the same manner as described in Example 1 except that 1-nitroso-2-hydroxy-3-meth-- acryloxymethyldibenzofuran was used instead of l-nitroso-2-hydroxydibenzofuran.
(2) Results of analysis Elementary analysis values: -Found Value (%) Calculated Value f%) C 74.4 74.7 H 5.5 5.6 N 6.1 6.0 IR: 1720 cm 1 (3) Application A glass sheet was prepared in the same manner as described in Example 7 by using the compound of the formula (N). When the glass sheet was irradiated with ultraviolet rays, the glass sheet became green, and when the light was Le,..o~ed and the glass sheet was allowed to stand in the dark, the glass sheet became colorless again.
ExamPle 22 (1) Synthesis of spiro-oxazine of following formula (O):

.~
~.c~

C2HSCH NJ ~ -C-NH(CH2 ) 20-C-C=CH2 ~1 ` ~s~) ( ) A solution comprising 15 g of 1-nitroso-2-~ydroxy-8-(N-methacryloxyethyl)carbamoyloxydibenzo-hiophene, 20 g of piperidine and 100 ml of richloroethylene was heated to the reflux temperature.
~hen, 9 g of 1,3-dimethyl-3-ethyl-2-methylene-indoline ~as added dropwise to the solution being refluxed over a 2eriod of 30 minutes. After the dropwise addition, reaction was carried out at the reflux temperature for 2 hours. After the reaction, the purification was carried out in the same manner as described in Example 1 to obtain a white crystal of the spiro-oxazine of the 'ormula (0).
(2) Results of analysis Elementary analysis values:
Found Value (%) Calculated Value (%) C 68.1 68.1 H 6.2 6.1 N 8.5 8.6 S 4.6 4.9 IR: 3330 cm 1, 1740 cm 1, 1717 cm 1, 1680 cm~l, 1540 cm 1 (3) Application When a solution of the compound of Example 22 in ~cetone was irradiated with ultraviolet rays, the -olution became red, and when the light was removed and he solution was allowed to stand in the dark, the -olution became colorless. Even when the above procedure was repeated 10 times, the photochromic characteristics were not changed at all.
Example 23 Synthesis of spiro-oxazine of following 5 formula (P):

1~'- ~ ~P~
CH3 C\2 CH=CH2 A milky white crystal of the spiro-oxazine of the formula (P) was obtained in Example 1 except that l-methyl-3-spirocyclohexyl-2-methylene-indoline was used instead of 1,3,3-trimethyl-2-methylene-indoline and 3-hydroxy-4-nitroso-9-(4-vinyl)benzylcarbazole was used instead of l-nitroso-2-hydroxydibenzofuran.
(2) Results of analysis Elementary analysis values:
Found Value (~) Calculated Value r%) C 82.5 82.6 H 6.0 6.3 N 7.9 8.0 (3) Application When a solution of the compound of Example 23 in acetone was irradiated with ultraviolet rays, the solution became red, and when the light was removed and the solution was allowed to stand in the dar~, the solution became colorless again. Even when the above procedure was repeated 10 times, the photochromic characteristics were not changed at all.
A

ExamPle 24 (1) Synthesis of spiro-oxazine of following formula (Q):
O
CH =HC-CHN C~3CH3 ~ ~ ~

2 ~ (Q) A light yellow crystal of the compound of the formula (Q) was obtained in the same manner as described in Example l except that 1,3,3-trimethyl-2-methylene-5-acrylaminoindoline was used instead of 1,3,3-tri-methyl-2-methylene-indoline and 8-hydroxy-9-nitroso(-1,2-benzodiphenylene oxide) was used instead of 1-nitroso-2-hydroxydibenzofuran.
(2) Results of analysis Elementary analysis ~alues:
_ Found Value (%~ Calculated Value (~) C 76.2 76.4 ~ 4.8 5.1 N 8.8 8.6 IR: 1675 cm 1 (3) Application When a solution of the compound of Example 24 in acetone was irradiated with ultraviolet rays, the solution became green, and uhen the light was removed and the solution was allowed to stand in the dark, the solution became colorless. Even when the abo~e procedure was repeated 10 times, the photochromic characteristics were not changed at all.
ExamPle 25 (1) Synthesis of 2-hydroxy-9-methylcarbazole To a mixture comprising 20 g of 2-hydroxy-CA rh~ 70le ~ 3 g of benzyltriethyl ammonium chloride, ~.

70 ml of a 50~ aqueous solution of sodium hydroxide and 10 ml of benzene was added dropwise 25 g of methyl iodide. After the dropwise addition, the mixture was stirred for 2 hours. The mixture was poured into hot water and the mixture was allowed to stand at room temperature overnight. The precipitated solid was recovered by filtration, washed with water and dried to obtain a yellowish brown solid of 2-hydroxy-9-methyl-carbazole.
(2) Synthesis of 1-nitroso-2-hydroxy-9-methyl-carbazole A red solid of l-nitroso-2-hydroxy-9-methyl-carbazole was prepared in the same manner as described in (1) of Example 1 except that the compound obtained in (1) above was used instead of 2-hydroxy~ihen7-ofuran.
(3) Synthesis of spiro-oxazine of following _ormula (R):

~ Y ~ / (R) A greenish white crystal of the spiro-oxazine of the formula (R) was prepared in the same manner as described in (2) of Example 1 except that the compound obtained in (2) above was used instead of 1-nitroso-2-hydroxy~ih~n~ofuran.
(4) Results of analysis of compound of formula (R) Elementary analysis values:
Found Value (%) Calculated Value (%) C78.7 78.7 H5.9 6.0 N10.8 11.0 (5) Application When a solution of the compound of Example 25 133~503 in acetone was irradiated with ultraviolet rays, the solution became red, and when the light was removed and the solution was allowed to stand in the dar~, the solution became colorless. Even when the above procedure was repeated 10 times, the photochromic characteristics were not changed at all.
Industrial APplicabilitY
Since the spiro-oxazine compound of the present invention has connected benzene, heterocyclic 5-membered and benzene (or naphthalene) rings, represented by a dibenzofuran ring, the spiro-oxazine compound of the present invention has absorptions in both the short wavelength region (less than 550 nm) having a yellow chromophoric seed and the long wavelength region (larger than 600 nm) having a blue chromophoric seed in the visible ray region. Accordingly, a green chromophoric seed not obtainable by the conventional technique can be realized, and an abundance of hues can be selected.
Therefore, the spiro-oxazine compound of the present invention is an epoch-making photochromic compound.
Furthermore, the fatigue resistance is good.
Accordingly, the compound of the present invention is valuable as an optical element such as sunglasses, ski goggles or protective glass lens, or a material for curt~i~ing, clothing, automobile windows, toys, writing tools, or rewritable optical disks.

Claims (6)

1. a spiro oxazine compound represented by the following formula (A) or (A'):

(A) or (A') wherein the .alpha. ring is a ring selected from the group consisting of a 5-membered ring having one nitrogen atom, a 5-membered ring having one nitrogen atom and connected to a benzene ring or naphthalene ring and a 6-membered ring having one nitrogen atom, with the proviso that the nitrogen atom in the .alpha. ring is bonded to an organic group R0 and is expressed as > N-R0 wherein R0 is a substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms and an aryl group having 6 to 19 carbon atoms; the .beta. ring is a benzene ring or a naphthalene ring; X is selected from the group consisting of O, S, Se and N-R1 wherein R1 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 19 carbon atoms and an acyl group having 2 to 20 carbon atoms; R2 and R3 are a substituent selected from the group consisting of a hydrogen atom, a hydroxyl group, an amino group having 0 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 14 carbon atoms, a halogen group, a cyano group, a carboxyl group, a nitro group, an acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a carbamoyl group having 2 to 20 carbon atoms, a carbamoyloxy group having

2 to 20 carbon atoms, and a sulfonic acid group, with the proviso that R2 is not a hydrogen atom, and R3 is not a nitro group; and k is a integer of from 0 to 2.
2. A spiro-oxazine compound represented by the following formula (B) or (B'):

(B) or (B') wherein R0, R2, R3, X and k are as defined in claim 1, R4 and R5 independently stand for a substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms and an aryl group having 6 to 19 carbon atoms, or R4 and R5 together form a cyclo-alkyl group having 3 to 10 carbon atoms with the carbon atoms at the 3'-position, R6 and R7 stand for a substituent selected from the group consisting of a hydroxyl group, an amino group having 0 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 14 carbon atoms, a halogen group, a cyano group, a carboxyl group, a nitro group, an acyl group having 2 to 20 carbon atoms, an alkoxyca-rbonyl group having 2 to 20 carbon atoms, a carbamoyl group having 1 to 20 carbon atoms, a carbamoyloxy group having 2 to 20 carbon atoms and a sulfonic acid group, and ? and m stand for an integer of from 0 to 4.

3. A spiro-oxazine compound represented by the following formula (C) or (C'):

(C) or (C') wherein R0, R2, R3, X and k are as defined in claim 1, R4 and R5 independently are selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms and an aryl group having 6 to 19 carbon atoms, or R4 and R5 together form a cycloalkyl group having 3 to 10 carbon atoms with the carbon atoms at the 3'-position, R6 and R7 are selected from the group consisting of a hydroxyl group, an amino group having 0 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 14 carbon atoms, a halogen group, a cyano group, a carboxyl group, a nitro group, an acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a carbamoyl group having 1 to 20 carbon atoms, a carbamoyloxy group having 2 to 20 carbon atoms and a sulfonic acid group, and ? and m are an integer of from 0 to 4, R8 is selected from the group con-sisting of a hydroxyl group, an amino group having 0 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 14 carbon atoms, a halogen group, a cyano group, a carboxyl group, a nitro group, an acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a carbamoyl group having 1 to 20 carbon atoms, a carbamoyloxy group having 2 to 20 carbon atoms and a sulfonic acid group, and n is an integer of from 0 to 2.

4. A spiro-oxazine compound represented by the following formula (D) or (D'):

(D) or (D') wherein R0, R2, R3, X and k are as defined in claim 1, R4 and R5 independently are selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms and an aryl group having 6 to 19 carbon atoms, or R4 and R5 together form a cycloalkyl group having 3 to 10 carbon atoms with the carbon atoms at the 3'-position, R6 and R7 are selected from the group consisting of a hydroxyl group, an amino group having 0 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 14 carbon atoms, a halogen group, a cyano group, a carboxyl group, a nitro group, an acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a carbamoyl group having 1 to 20 carbon atoms, a carbamoyloxy group having 2 to 20 carbon atoms and a sulfonic acid group, and ? and m are an integer of from 0 to 4, R8 is selected from the group consis-ting of a hydroxyl group, an amino group having 0 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 14 carbon atoms, a halogen group, a cyano group, a carboxyl group, a nitro group, an acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a carbamoyl group having 1 to 20 carbon atoms, a carbamoyloxy group having 2 to 20 carbon atoms and a sulfonic acid group, and n is an integer of from 0 to 2.

5. A spiro-oxazine compound represented by the following formula (E) or (E'):

(E) or (E') wherein R0, R2, R3, X and k are as defined in claim 1, R4 and R5 independently are selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms and an aryl group having 6 to 19 carbon atoms, or R4 and R5 together form a cycloalkyl group having 3 to 10 carbon atoms with the carbon atoms at the 3'-position, R6 and R7 stand for a substituent selected from the group consisting of a hydroxyl group, an amino group having 0 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 14 carbon atoms, a halogen group, a cyano group, a carboxyl group, a nitro group, an acyl group having 2 to 20 carbon atoms, an alkoxycar-bonyl group having 2 to 20 carbon atoms, a carbamoyl group having 1 to 20 carbon atoms, a carbamoyloxy group having 2 to 20 carbon atoms and a sulfonic acid group, and ? and m are an integer of from 0 to 4, R9, R10, R11, R12, R13 and R14 are selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 19 carbon atoms.

6. A spiro-oxazine compound represented by the following formula (F) or (F'):

(F) or (F') wherein R0, R2, R3, X and k are as defined in claim 1, R4 and R5 independently are selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms and an aryl group having 6 to 19 carbon atoms, or R4 and R5 together form a cycloalkyl group having 3 to 10 carbon atoms with the carbon atoms at the 3'-position, R6 and R7 stand for the group consisting of a hydroxyl group, an amino group having 0 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 14 carbon atoms, a halogen group, a cyano group, a carboxyl group, a nitro group, an acyl group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, a carbamoyl group having 1 to 20 carbon atoms, a carbamoyloxy group having 2 to 20 carbon atoms and a sulfonic acid group, and ? and m stand for an integer of from 0 to 4, R15 is selected from the group consisting of a hydroxyl group, an amino group having 0 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aralkoxy group having 7 to 15 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 15 carbon atoms, an aryl group having 6 to 14 carbon atoms, a halogen group, a cyano group, a carboxyl group, a nitro group, an alkoxycarbonyl group having 2 to 20 carbon atoms, a carbamoyl group having 1 to 20 carbon atoms, a carbamoyloxy group having 1 to 20 carbon atoms and a sulfonic acid group, and t is an integer of from 0 to 2.