DE2239877C3 - Benzo pyranyliden-propenylbenzopyrylium perchlorate or Benzothiapyranylidenpropenylbenzothiapyrylium perchlorate and their use as sensitizers for organic photoconductors - Google Patents

Description

2- [3 '- (3 "-Phenyl-2" -benzopyranylidene) -

propenylJ-3-phenylbenzopyrylium-

perchlorate

2- [3 '- (3 "-Phenyl-8" -methoxy-2 "-benzo-

pyranylidene) propenyl] -3-pbenyl-

8-methoxybenzopyrylium perchlorate 2- [3 '- (3 "-Phenyl-6" -methoxy-2 "-benzo-

pyranylidene) propenyl] -3-phenyI-

6-methoxybenzopyrylium perchlorate 2- [3 '- (3 "-Phenyl-6" -nitro-2 "-benzopyranylidene) propanyl] -3-phenyI-

6-nitrobenzopyrylium perchlorate 2- [3 '- (4 "-p-methoxyphenyl-2" -benzo-

pyranylidene) propenyl] -4-p-methoxy-

phenylbenzopyrylium perchlorate 2- [3 '- (3 "-phenyl-4" -p-methoxyphenyl-2 "-benzopyranylidene) propenyl] -S-phenyl 1-4 -p-methoxyphenylbenzopyrylium perchlorate

2- [3 '- (3 ", 6" -Diphenyl-4 "-p-methoxyphenyl-2" -benzopyranylidene) propenylI -3,6-diphenyl-4-p-methoxyphenylbenzopyrylium perchlorate

2- [3 '-! 4 "- (4'" - methoxynaphthyl (l '")) - 2" -benzopyranylidene} -propenyl] -4- (4'-methoxynaphthyl ( 1 ')) - benzopyrylium perchlorate

2- [3 '- {3 "-i'henyl-4" - (4' "- methoxynaphthyl (l" ')) - 2 "-benzopyranylidene! - propenyl] -3-phenyl-4- (4'-mei; hoxynaphthyl (1 '»benzopyrylium perchlorate 2- [3 '- {3 ", 6" -Diphenyl-4 "- (4" -methoxynaphthyH 1' ")) - 2" -benzopyranylidene} -propenyl] 3,6-diphenyl-4- (4'- methoxynaphthylO )) benzopyrylium perchlorate 2- [3 '- {4 "- (2"' - methoxynaphthyl (l "')) - 2" -benzopyranylidene} -propene \ I] -4- (2'-methoxynaphthyl (1 ')) benzopyrylium perchlorate

2- [3 '- {3 "-PhenyI-4" - (2' "- metlioxy-

naphthyl (l '")) - 2" -benzopyranylideni-

propenyl] -3-pheny] -4- {2'-methoxy-

naphthyl (l '»benzopyrylium perchlorate 2- [3' -! 3", 6 "-diphenyl-4" - (2 '"- methoxy-

naphthyl (r ")) - 2" -benzopyranylidene} -

propenyl] -3.6-diphenyl-4- (2'-methoxy-

naphthyl (1 '»benzopyryliumpcrchloral 2- | 3' - (4" -p-methoxyphenyl-2 "-benzo-

thiapyrany! iden) propcnyl] -4-p-melhoxy-

phenylbenzolhiapyrylium perchlorate 2- [3 '- (3 "-Phenyl-4" -p-methoxyphenyl-2 "-bcnzothiapyranylidene) propenyl] - 3-phcnyl-4-p-methoxyphenyl benzothiapyrylium perchlorate

connection

No.

2- [3 '- (3 ", 6" -Diphenyl-4 "-p-mothoxyphenyI-2" -benzothiapyranylidene) -propenyl] -3,6-diphenyl-4-p-methoxyphenylbenzothiapyrylium perchlorate 2- [3 '-! 4 "- (4"' - methoxynaphth \ l (1 '") -2" -benzoihiapyranylidene] -propenyrj-4- (4'-methoxynaphthyI ( 1 ')) - benzothiapyrylium perchlorate

2- [3'-13 "-Phenyl-4" - (4 '"- methoxynaphthyl (1'")) -2 "-benzothiapyr; ^j .nyiiden (-propenyl] -3-phenyl-4- (4'- methoxynaphthyl (1 ')) benzo- (hiapyry) iumperchloral

2- [3 '-! 3 ", 6" -Diphenyl-4 "- (4'" - methoxynaphthylf 1 "')) - 2" -benzothiapyranylidene | - propenyl] -3,6-diphynyl-4- (4'-melhoxynaphthyl ( 1 ')) benzolhiapyrylium perchlorate

2- [3'-14 "- (2 '" - methoxynaphthyl (r ") | - benzothiapyranylidene] propynyl] -4- (2'-methoxynaphthyl ( 1 ')) benzothiapyrylium perchlorate

2- [3'-13 "-Phenyl-4" - (2 "'- methoxynaphthyl (l'")) - 2 "-bcnzothiapyranyliden! - propenyl] -3-phenyl-4- (2'-methoxynaphyl (r)) benzothiapyrylium perchlorate

2- [3 '-! 3 ", 6" -Diphenyi-4 "- (2'" -methoxynaphthyl (1 '")) -2" -benzothiapyranylidcn; -propenyl] -3.6-diphenyl-4- (2'- melhoxynaphthyl (l ')) benzothiapyrylium perchlorate

2- [3 '- (2 "-Benzopyranylidene) propenyl] benzopyrylium perchlorate 2- [3 '- (3 ", 6" -Diphcnyl-2 "-benzopyranylidene) propenyl] -3,6-diphenylbenzopyrylium perchlorate.

2. Use of the Benzopyranyliden-propenylbenzopyryliumperchlorate or Benzothiapyranyliden - propenylbenzothiapyryliumperchlorale according to claim 1 as sensitizers for organic Photo splitter made of poly-N-vinylcarbazole. bromicrtem Poly-N-vinylcarbazole or polyaccnaphthylene.

The invention relates to the following Benzopyranylidenpropenylbenzopyryliumpeichlorate or Bcnzothiapyranyliden-propenylbenzothiapyryliumperchlorate:

Vcr-Ηίηϋιιημ

2- [3 '- {3 "-Phcnyl-2" -bcnzopyranylidene) -propenylJ-3-phenylbcnzopyryliuiii-

ncrchlorate

continuation

indung

ι 2- [3 '- (3 "-Phenyl-8" -methoxy-2 "-benzo-

pyranylidene) propenyl] -3-phenyl-K-nu'ihoxybenzopyrylium perchlorate

2- [3 '- (3 "-Phenyl-6" -methoxy-2 "-benzo-

pyranylidene} propenyl] -3-phenyl-6-methoxybenzopyrylium perchlorate

2- [3 '- (3 "-Phenyl-6" -nitro-2 "-benzopyranylidcn) propanyl] -3-phenyl-6-nitrobenzopyrylium perchlorate

2- [3 '- (4 "-p-Mclhoxyphenyl-2' -benzopyranylidene) propenyl] -4-p-methoxyphenylbenzopyrylium perchlorate

2- [3 '- (3 "-Phenyl-4" -p-mc: thoxyphynyl-2 "-benzopyranylidene) propynyl-3-phenyl-4-p-methoxyphynylbenzopyrylium pcrchlorate

2- [3 '- (3 ", 6" -Diphcnyl-4 "-p-mcihoxyphcnyl-2" -benzopyranylidene) propenyl] -3,6-diphenyl-4-p-mcthoxypheΓιylbenzopyryliumpcrchlorat

g 2- [3 '-! 4 "- (4'" - methoxynaphthyl (1 '")) -

2 "-benzopyranylidene | -propenyl] -4- (4'-methoxynaphthyl ( 1 '' benzopyrylium perchlorate

2- [3 '- {3 "-Phenyl-4" - (4' "- methoxynaphthyl (l" ')) - 2 "-benzopyranylidene! - propenyl] -3-phenyl-4- (4 '-methoxynaphthyK 1')) benzopyrylium perchlorate

2- [3 '- {3 ", 6" -Diphenyl-4 "- (4" -methoxy-

naphthyl (r ")) -2" -benzopyranylidene [-propenyl] -3,6-diphenyl-4- (4'-methoxynaphthyl (r)) benzopyrylium perchlorate

Π 2- [3'- | 4 "- (2 '" - Mclhoxynaphthyl (r ")) -

2 "-benzopyranylidcn [-propenyl] -4- (2'-methoxynaphthyl (1. ')) Benzopyrylium perchlorate

2- [3 '- {3 "-Phenyl-4" - (2' "- melhoxynaphthyl (r")) -2 "-benzopyranylidcn | - propenyl] -3-phenyl-4- (2'-methoxynaphthyK 1 ')) benzopyrylium perchlorate 2- [3 '- {3 ", 6" -Diphcnyl-4 "- (2'" -methoxynaphthyl (1 "')) - 2" -benzopyranyliden; -propcnyl] -3,6-diphenyl-4- (2 '-methoxynaphthyl (1')) benzopyrylium perchlorate

2- [3 '- (4 "-p-Methoxyphenyl-2" -bcnzothiapyranylidene propenylj ^ l-p-Incthoxyphynylbenzothiapyryliumpcrchlorat

2- [3 '(3 "-Phcnyl-4" -p-melhoxyphenyl-2 "-benzothiapyranylidcn) propenyl] -S-phenyl ^ -p-mclhoxyphynylbcnzolhiapyryliumpcrchlorai

2- [3 '- (3 ", 6" -Diphcnyl-4 "-p-mcihoxyphcnyl-2" -ben / othiapyranylidene) propenyl] -S.o-diphenyl-i-p-methoxyphynylbcn / oiliiapyryliumpcrchloriil

2- | 3 '-! 4 "- (4"' - Mcthoxynaphihyl (l '") - 2" -bcnzolliiapyranylidcn! -Propcnyl ") - 4- (4'-mcthoxynaphlhyi ( 1 ')) - bcnzothiapyrylium perchloral

Connection

No.

2- [3 '-; 3 "-Phenyl-4" - (4 "' - methoxynaphthyl (l"')) - 2 "-benzothiapyranylidene! -
propenyl] -3-phenyl-4- (4'-methoxynaphthyl (r)) benzothiapyrylium pcrchlorate

2- [3 '-! 3 ", 6" -Diphenyl-4 "- (4" -mcthoxynaphthyl (r ")) - 2" -benzothiapyranyliden! -
propynyl] -3,6-diphenyl-4- (4'-meth'oxynaphyl (l ^r )) benzothiapyrylium perchlorate

2- [3 '-! 4 "- (2'" - Mcihoxynaphthyl (r ") | -
benzothiapyranylidene-propenyl] -4- (2'-methoxynaphthyl (Γ »benzothiapyrylium pcrchlorate

2- [3 '-! 3 "-Pbeny] -4" - (2' "-methoxynaphthyl (r")) -2 "-benzothiapyranylid-propenyl] -3-phenyl-4- (2'-methoxynaphthylf 1 'Dbenzothiapyrylium pcrchlorai

2- [3 '-; 3 ", 6" -Diphcnyl-4 "- (2"' - methoxy-

naphlhyl (l '")) - 2" -benzothiapyranylidcn! -

propenyl] -3,6-diphcny! -4- (2'-methoxy-

naphthyld'Dbcnzothiapyryliunipcrchlorai

2- [3 '- (2 "-Benzopyranylidcn) propynyl] -

benzopyrylium perchlorate

2 - [. 3 '- (3 ".6" -Diphcnyl-2 "-benzo-

pyranilidcn) propenyl] -3.6-diphenylbcn / ,. i-

pyrylium pcrchlorai.

as well as their use as sensitizers lür organic photoconductors made from poly-N-vinylcarba / ol. bromieriem Poly-N-vinylearbazole or polyacenaphthylene.

Many types of organic photoconductive layers are used in electrophotographic to make copies of documents. Drawings. Look-through images known. For the clekirophoiographisehe technique it is necessary that the photolcitende Layer a strong wedge of conductivity in the long wavelength range of the visible spectrum or in the near infrared wavelength range. Such a photoconductive layer makes it in the field the electrophotographic possible, cheap and convenient Light sources such as B. a tungsten filament. to use with a shortened exposure time.

In addition, organic molecules are of interest in the fields of electronic engineering, computers, and high-speed technology Recording and investigation systems. The above areas require a highly sensitive one and transparent organic photoconductors. preferably a film-forming organic Phoiolciter.

Known organic phntoconductors are, for example, Pol v-N-vi nylcarba / .ol. halogenieries poly-N-vinylcarba / ol. Polyacenaphthylene. Polyvinyl anthracene. The layers that make up these photoconductive polymers contained, are dielectrics of electrical energy before exposure and become electrical after exposure Ladder.

It is also known that the photoconductivity and the spectral characteristics of the above Pholeiier can be improved by adding a sensitizer. Usual sensitization

lorcn are ζ. Β. Xanthene dyes. Triarylmethane dyes. Acridine dyes, carbocyanine dyes «:. However, these conventional sensitizers are not with regard to the improvement of the photoconductive capacity and the spectral characteristics of the photoconductor completely satisfactory.

The benzopyranylidenepropenylbenzopyrylium perchlorate according to the invention or Benzothiapyranyliden - propcnylbenzothiapyryliumpcrchloratc are now sensitizers Poly-N-vinylcarbazole photoconductor. bromicrtem Poly-N-vinylcarbazole or polyacenaphthylcn one high photoconductivity and the photoconductive layer a high sensitivity in the long-wave In the visible spectrum or in the near infrared wavelength range.

Preferably, the sensitizer of the present invention is used in an amount of 0.01 to 5.0 parts by weight to 100 parts by weight of the organic photoconductor concerned and in particular in an amount of 0.1 to 2.0 parts by weight per 100 parts by weight of the organic photoconductor in question.

The effect of the compounds according to the invention as sensitizers compared to known sensitizers was tested in the experiments below.

The poly-N-vinylcarbazole and polyacenaphthylene used here have been produced by processes known per se, while the brominated poly-N-vinylcarbazole used has been produced as follows: A solution of 20 g of poly-N-vinylcarbazole in 450 ml of chlorobenzene is 18, 44 g of N-bromosuccinimide and 0.173 g of benzoyl peroxide were added. ^{The mixture is heated at 80 °} C. for 2 hours with stirring and then poured into methanol, a white polymer being obtained. For purification, the polymer is dissolved in chlorobenzene and poured again into methanol. The pure polymer obtained as a precipitate has, according to the elemental analysis, a bromine content of 29.87 percent by weight, which is the calculated value. ie 39.44 weight percent of the monobromo-substituted product of the poly-N-vinylcarbazole. comes close, from which it can be seen that the polymer obtained is a monobromo-substituted product. The degree of bromination varies depending on the reaction conditions between 50 and 200 mol%.

Attempt 1

1 g of polyacenaphthylene and 0.6 g of chlorinated diphenyl as plasticizers are dissolved in 8 ml of chlorobenzene solved. To this solution, 0.5 ml of dichloroethane is added, the 0.006 g of the test according to the invention or known compound contains as a sensitizer. The solution is applied to an aluminum plate using the centrifugal application method. gene and dried to form a layer with a thickness of 7 μίτι. Then the one with the Layered aluminum plate by a corona discharge with a charger that is at approximately 6000VoIt is held, negatively charged in the dark, then under a positive original arranged and with a 100 W tungsten lamp exposed to an illuminance of 50 lux. The plate is then coated with a developing powder is sprayed over in a known manner. This developer consists of a toner and a carrier. The toner consists of polystyrene with a low melting point, k'nnnhonium and carbon black. The toner comes with a Carrier material mixed, so that the toner on triboclonic Way is charged with a charge opposite to the charge generated on the plate is. A positive image is created and fixed by gently heating. In the following Table 1 shows the sensitivity, which is defined as half-exposure in the unit lux · s is. this half-exposure representing the exposure through which a surface potential of the photoconductive layer drops to half the surface potential in the dark. The smaller one Half exposure represents greater sensitivity.

Table 1

Tested connection no. Halbwerlsbclichiunp E _5l , | Lux ■ s) None 200,000 2 380 7th 270 150 11th 160 18th 60 22nd 410 24 160 Crystal violet (known) 2 280 (Color index No. 42 555) Rhodamine 6G (known)
(Color index No. 45 160) 27 600 3.3'-diethyl-2,2'-thiacarbo-
cyanine iodide (known from the
by Nippon Kanko Shikiso
Kcnkyusho published
Catalog »Dyes for Photo« [1972]) 44,000

Attempt 11

1 gram of poly-N-vinyl carbazole. 0.5 g of chlorinated diphenyl and 0.006 g of the compound to be tested according to the invention or known as a sensitizer are dissolved in 10 ml of dichloroethane. The solution is applied as a layer to a polyester film (with a thickness of 0.1 mm) with a transparent, conductive copper (l) iodide layer using a doctor blade and dried to form a layer with a thickness of 10 μm. ^p in electrophotographic image is formed in the same manner as described in Experiment 1. The following table 2 shows the sensitivity, expressed as half-value exposure in the unit lux · s.

Table 2

Tested connection no.

None

Haibwcrlsbclichlunc

E _w (Lux ■ s)

20,000

8.3

10.1

8.8

6.2

continuation

Tested connection no

Illuminating
E ₅₀ (LuX-S)

8th 6.9 Il 8.4 22nd 16.0 23 20.0 24 7.0 Crystal violet 120 Rhodamine 6G 220 3,3'-diethyl-2.2'-thiacarbo- 4,560 cyanine iodide

25th

The graphs of absorption spectra of poly-N-vinylcarbazole films. those with the following indicated compounds according to the invention sensitized are shown in FIGS. 2 to 4 shown.

This was poly-N-vinylcarbazole and the relevant Sensitizer dissolved in dichloroethane, the solution on a glass plate with an electrically conductive Layer applied, and the solvent evaporates, so that a sensitized photoconductive layer with a thickness of 10 μίτι made of poly-N-vinylcarbazole was obtained. The concentration of the sensitizer in the poly-N-vinylcarbazole was 0.2 mole percent. the

F i g. Fig. 2 shows the absorption spectrum of the film sensitized with Compound No. 15; the

F i g. Fig. 3 shows the absorption spectrum of the film sensitized with Compound No. 1: die

F i g. 4 shows the absorption spectrum of the Compound No. 19 sensitized film.

In addition, the above-obtained sensitized film with Compound No. 15 was then made as follows treated:

Aluminum was vapor-deposited on the parallel surface of the layer as an electrode, a conductive cell (cell of the "sandwich" type) being obtained. The surface area of the aluminum electrode is 0.3 cm ² . The cell is exposed to a light which has a maximum at an absorption maximum of the sensitizer. The light is obtained from a xenon lamp with an interference filter. The electrical voltage applied to the cell is varied.

The photocurrent increases almost linearly with the applied electric field up to 2 10 ⁴ V cm. The photocurrent is proportional to the intensity of the light.

The spectral sensitivity distribution of the photocurrent will be in a range from 400 to 1000 mum measured with a xenon lamp and a monochromator. In FIG. 5 is the spectral diagram Sensitivity distribution of the cell of the photoliter sensitized with compound no. 15 is given. The electrical voltage applied to the cell is a DC voltage of 20 V.

Experiment III

1 g bromicrtcs poly-N-vinylcarbazole. the same as above stated, 0.5 g of polycarbonate resin. 0.3 g of chlorinated diphenyl and 0.002 g of the sensitizer to be tested are in a solvent mixture dissolved from 8 ml of chlorobenzene and 2 ml of dichloroethane. This solution is applied to a polyester film (with a thickness of 0.1 mm) with a transparent, conductive copper (I) -jodidschichl by means of a Squeegee applied as a layer and dried to form a layer 10 µm thick. on In the same way as described in Experiment 1, this substrate becomes an electrophotographic Image generated. In the following Table 3, the sensitivity is expressed in terms of half-value exposure in the unit Lux ■ s, reproduced.

Furthermore, the relative decay half-value line is determined (in arbitrarily selected units) of the above-described sensitized layer with brominated poly-N-vinylcarbazole for a light filtered with a specific filter. For this purpose, the filtered light was obtained from a tungsten lamp which was provided with light filters No. 25, 47 and 58. The filter No. 25 allowed light with the wavelength range from 600 to 700 ΐτίμΓη through. The filter No. 41 let light with the wavelength range of 400 bi; 500 mum through. The. Filter No. 58 was light mi the Wellenlängcnbereich of 500 to 600 mum by The thus obtained results are summarized in Table ^L.

35

40

45

5 °

60

Table 3 Half-life cakes Connection no. E ₅₀ (LuX s) 80,000 None 4.7 1 6.1 Z 7.8 3 4.7 4th 7.5 5 15.0 6th 4.0 7th 11.0 8th 38.0 9 17.0 10 7.8 11th 10.0 12th 10.0 13th 6.4 14th 15.0 15th 9.5 16 11.0 17th 8.0 18th 10.0 19th 24.0 20th 18.0 21 18.0 22nd 15.0 23 4.6 24 4,800 Crystal violet 2,760 Rhodamine 6G 7 920 3,3'-diethyl-2,2'-thiacarbo- cyanine iodide

609 608

Table 4

Connection no.

Relative decay half-life in arbitrarily chosen units

Crystal violet
Rhodamine 6G

SJ'-diethyl - ^ '- thiacarbocyanin iodide

using the filter

No. 25.

0.2 0.5 3.6

340

996 1200

using the three filters 25. 47 and 58

27.6 2.6 9.9 2360 1280 3200

Example 1 g of 2-methyl-3-phenylbenzopyrylium perchloral are dissolved in 200 ml of acidic anhydride. After the addition of 19 g of ethylhorormate, the solution is stirred at 100 ° C. for minutes. After the solution has cooled to room temperature, the solution is slowly poured into 2 l of 10% strength perchloric acid, a precipitate being formed. The precipitate is filtered off, dried, washed with 300 ml of acetonitrile and dried again. Fs 7 g of 2- [3 '- (3 "-Phcnyl-2" - benzopyranylidenlpropenyl I - obtained in the form phenylbcnzopyryliumperchiorai länzcndcr "crystals 253-255 ¹ C The compound has an absorption maximum at in Dichlorälhan and 706 mum - 3..

In the same manner, using the respective reactants, the following were made Connections made with the specified data:

Connection no.

The values in Tables 1 to 4 show that the compounds according to the invention in comparison improve the photoconductivity considerably in addition to the known sensitizers.

The diagrams of gray wedge spectroscopy of a electrophotographic material coated with a solution. the 10 weight percent of the brominated poly-N-vinylcarbazole used in experiment III contains, in a solution medium mixture of 4 parts by weight of chlorobenzene and 1 part by weight Dichloroethane has been dissolved and that with 0.04 percent by weight of the cr according to the invention given below Compound sensitized are shown in the fig. 6 to 9 shown. the

F i g. Figure 6 shows the gray wedge spectrogram of the material sensitized with Compound No. 15: die

Fig. 7 shows the gray wedge spectrogram with Compound No. 24 of sealed material; the

Fig. 8 shows the gray wedge spectrogram with of Compound No. 19 Sensitizable Material: the

Fig. 9 shows the gray wedge spectrogram of the with Compound No. I of Sealed Material.

The above-mentioned benzopyranylidene-propenylbenzopyrylium perchlorates or _4S Benzothiapyranylidcn-propenylbenzothiapyrylium perchlorates are prepared by adding, in a manner known per se, the corresponding 2-methylbenzopyrylium perchloride or the corresponding 2-methylbenzothiapyrylium perchlorate with an in reacted and then "treated the reaction product with perchloric acid.

It is preferred to work at 50 to 110 ° C

55

2- [3 '- (3 "-Phenyl-2" -benzopyranylidane) propenyl] -3-phenyl-benzopyrylium perehlorate

(Connection 1)

CH = CH - CH

ClO, melting point

25 3 4 5 6 7 8 9 10 11 12 13 14 16 17 18 19 20

21

23 24 (C)

280

283—

194—

150-241

> 300
247-232-
198
226
230-238-
159—
200-219
232-184-220-163-

> 300

282 285 198 153 243

250 234 202 229 233 241 161 261 261

Tl-,

238 235 186 223 168

Absorption maximum in dichloroethane

(ηΐμηι)

652 and

679 and

645 and

667 and

664 and

683 and

714

666 and

681 and

704

659 and

679 and

7 ^ 2

854

781

830

857

777

818

850

690

670 and

example

-; [ ³ - (- ^v '-Phcnyl-4 "-p-methoxyphenyl-2" -benzothiapyranylidene) -propenyl] -3-pnenyl-4-p-methoxy-

Phenyl benzothiapyrylium perchlorate (compound no.15)

/ T _x

/ S;

CH = CH-CH

OCH,

OCH,

ClO ₄

4.4 g of 2 - methyl - 3 - phenyl - 4 - ρ - methoxyphenylbenzopyrylium perchlorate (F .: 212 to 213 C). which have been obtained by a Grignard reaction of 2-methyl-3-phenylbenzothiachromone with p-methyl-oxyphenylmagnesium bromide are dissolved in 80 ml of acetic anhydride. After addition of 3.8 g Äthylorthoformiai the solution is stirred for 15 minutes at ¹ OO C. After the solution has cooled to room temperature, the solution is slowly poured into 400 ml of 10% perchloric acid, a precipitate being formed. The precipitate is filtered off, dried, dissolved in dichloroethane and washed with ethyl ether

failed again. There are 6 g of 2- [3 '- (3 "-Phenyl-4" - ρ - methoxyphenyl - 2 "- benzothiapyranyliden) -propenyl] - 3-phenyl -4-p-methoxyphenyl-benzothiapyrylium perchlorate in the form of fine crystals obtained from F. 176 to 179 C.

The absorption spectrum of 2- [3 '- (3 "-phenyl-4" - ρ - methoxyphenyl - 2 "- benzothiapyranyliden) -propenyl] - 3 - phenyl - 4 - ρ - methoxyphenylbcnzothiapyrylium - perchlorate in Dichloräthanlösum (1.26-10 ^-5 Mol / l) is shown in Fig. 1. Da; the absorption maximum in dichloroethane is 827 ηΐμίη.

For this purpose 4 sheets of drawings

Claims (1)

Patent claims: I. Benzopyranylidene - propenylbenzopyrylium perchlorate or Benzothiapyranyliden-propeny! - bcnzolhiapyryiiumperchiorate as follows: connection
No.