JP3158631B2 - Nonlinear optical material comprising 1,4-dioxa-8-aza-8- (4'-acetylphenyl) -spiro [4,5] decane - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an optical parametric oscillation,
Harmonic generation, key 1 in the optical signal processing systems, such as optical switching, 4-dioxa-8-aza-8- (4 '
- acetylphenyl) - it relates nonlinear optical material using spiro [4,5] dec down.

[0002]

2. Description of the Related Art Nonlinear optical materials, which are expected to play an important role in the field of optical communication and the like, exhibit functions such as optical mixing, parametric oscillation, and optical harmonic generation based on the nonlinear response of the material. Conventionally, KH ₂ PO ₄ , NH ₄ H ₂
Inorganic crystals such as PO ₄ have been used. However, these materials do not meet the aforementioned requirements due to deliquescence, low nonlinear susceptibility and low destruction threshold. Also, the primary and secondary electro-optic effects that can be used for optical switching are effects that result from essentially the same nonlinear polarization as the secondary and tertiary nonlinear optical effects, respectively. There is. Since the response speed of the inorganic material as described above is low, the frequency band is narrowed. Organic nonlinear optical materials using π-electron polarization have been studied extensively in various fields because their nonlinear optical constants are superior to inorganic materials, and they are generally excellent without deliquescent and high destruction threshold. Development is underway. For recent achievements, see, for example, "Nonnia Optical Properties of Organic Molecular and Crystals" (Nonlinear
Optical Properties of Or
ganic molecules and cryst
als) Vol. 1 and Vol. 2, D. S. Chem
la, J. et al. Zyss ed. (1987 Academic
Press).

However, a material having a large nonlinear optical constant such that a low output laser can sufficiently achieve its purpose, such as a semiconductor laser, has not been found, and further development of a new material is strongly demanded.

[0004]

[SUMMARY OF THE INVENTION The present invention provides a nonlinear optical material using a lifting one of compound large nonlinear optical constant.

[0005]

SUMMARY OF THE INVENTION The present invention is 1,4-dioxa-8-aza-8-formula [I] (4'-acetylphenyl) - spiro [4,5] dec-down or al And a non-linear optical material comprising a composition containing the compound.

Embedded image

The 1,4-dioxa-8-aza-8- (4'-acetylphenyl) -spiro [4,5] decane represented by the above formula [I] according to the present invention is, for example, 4-fluoro Acetophenone and 1,4-dioxa-8-azaspiro [4,5] decane can be synthesized by heating and refluxing in a solvent such as N, N-dimethylacetamide or dimethylsulfoxide in the presence of a base.

Further, the nonlinear optical material according to the present invention comprises 1,4-dioxa-8-aza-8- represented by the above formula [I].
(4'-Acetylphenyl) -spiro [4,5] decane may be used alone or a composition in which this compound is dispersed or dissolved in a polymer compound. As the polymer compound, for example, methyl (meth) acrylate (indicating methacrylate or acrylate; the same applies hereinafter), ethyl (meth) acrylate, n-butyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid, Styrene, vinyl toluene,
Homopolymers, copolymers or terpolymers of monomers such as divinylbenzene, vinyl chloride, β-hydroxyethyl (meth) acrylate, etc., polyesters, polyamides, polyurethanes, polycarbonates, cellulose esters, polyethers and the like are used. The compound represented by the formula [I] and the corresponding monomer may be mixed and then polymerized by the action of heat or light to form a composition. The composition may be obtained by dissolving and mixing using a suitable solvent and then removing the solvent. In the former case, the non-linear optical performance can be improved by performing poling during polymerization, or by performing poling after obtaining the composition for both the former and the latter. Alternatively, the compound of formula [I] is heated to a temperature equal to or higher than the melting point in the presence of a DC electric field, melted, and then gradually cooled or quenched while maintaining the electric field to control the molecular orientation state. High performance single crystal or molecular glass can also be obtained.

The above-mentioned nonlinear optical material can be used as a bulk crystal independently or in a fiber type, a slab type, a planar type,
It can be used as a part of a waveguide type optical element such as a channel type. Examples of the nonlinear optical element using the above nonlinear optical material include a wavelength conversion element using second harmonic generation, sum frequency generation or optical parametric oscillation, a phase modulation element using the electro-optic effect, and a polarization plane modulation element. .

[0009]

The compound of the present invention has a carbonyl group as an acceptor group and a tertiary amino group as a donor substituent. Since these are in the para position, they are conjugated via a benzene ring π-electron system and charge transfer in an excited state. As a result, a large dipole moment is generated, which has a high hyperpolarizability, thereby obtaining a high nonlinear optical effect.

[0010]

EXAMPLES The present invention will be described in more detail with reference to Examples. Synthesis of 1,4-dioxa-8-aza-8- (4′-acetylphenyl) -spiro [4,5] decane 1.381 g of 4-fluoroacetophenone (10 mmol)
l), 1,432 g of 1,4-dioxa-8-aza-8- (4'-acetylphenyl) -spiro [4,5] decane
(10 mmol), 5 ml of dimethyl sulfoxide and 1.382 g (10 mmol) of potassium carbonate in 50 ml
The mixture was heated at 50 ° C. for about 18 hours with a cooling condenser while stirring well using a magnetic stirrer. When 100 ml of cold water was added, crystals appeared. This was filtered and washed well with water.
The yield was 1.544 g (59.1%). The structure of the product was confirmed by nmr and absorption spectrum. FIG. 1 shows an ultraviolet-visible absorption spectrum of a methylene chloride solution of this compound.
FIG. 2 shows the nmr spectrum of the deuterated chloroform solution.

Comparative Examples, Examples The absorption maximum wavelength (λ) of 1,4-dioxa-8-aza-8- (4′-acetylphenyl) -spiro [4,5] decane
_max , methylene chloride solution) and the second determined by the powder method.
Table 1 shows the harmonic generation efficiency (SHG efficiency, the intensity ratio of the second harmonic when urea is 1) and the melting point. The outline of the powder method is described in Journal of Applied Physics.
cs) vol. 36 (1963) 3798-3813
It is detailed on the page. A sample powder classified to a particle size of 100 to 125 μm is sandwiched between non-fluorescent glass slides (manufactured by Matsunami Glass) and pulsed Nd: YAG laser manufactured by Spectro Laser System (SL303, maximum output 850 m).
J, a half width of 15 ns, an output per pulse of 60 MW, a beam diameter of 9.5 mm, a wavelength of 1.064 μm, and a repetition frequency of 10 Hz). The intensity of the generated 532 nm second harmonic was measured by a photomultiplier through an infrared filter and a UV filter.

[0012]

[Table 1]

According to the novel compound of the present invention, a nonlinear optical material having high optical nonlinearity can be obtained.

[Brief description of the drawings]

FIG. 1 shows 1,4-dioxa-8-aza-8 obtained in Examples
It is an ultraviolet-visible absorption spectrum of a methylene chloride solution of-(4'-acetylphenyl) -spiro [4,5] decane.

FIG. 2 shows 1,4-dioxa-8-aza-8 obtained in the example.
It is an nmr spectrum of a heavy chloroform solution of-(4'-acetylphenyl) -spiro [4,5] decane.

Continuation of the front page (56) References JP-A-60-34950 (JP, A) European Patent Application Publication No. 415816 (EP, A1) Synthesis, Vol. 8 (1981), p. 606-608 (58) Field surveyed (Int. Cl. ⁷ , DB name) G02F 1/35-1/361 C07D 491/056 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A 1,4-dioxa compound represented by the formula [I]
A non-linear optical material comprising 8-aza-8- (4'-acetylphenyl) -spiro [4,5] decane. Embedded image 2. A 1,4-dioxa-8-aza-8-
A nonlinear optical material comprising a composition containing (4'-acetylphenyl) -spiro [4,5] decane.