An antibacterial composition that comprises as active compound at least one light isotope of an element selected from the group which consists of 1H, 12C, 16O, 14N, 39K, 24Mg, 64Zn, 85Rb, 28Si, 54Fe, 92Mo, 74Se, 58Ni, 70Ge, 52Cr, 63Cu, 50V, or combinations thereof, wherein the composition is enriched for the at least one light isotope. A method of treating and preventing bacterial diseases in humans and non-human animals by administering the composition. The use of the said composition in human and veterinary medicine for the prevention and treatment of diseases in humans and non-human animals and also as an antiseptic and disinfectant.

The variability of isotopes is known as the isotope effect, a term describing the mass-dependent variations of natural isotope contents for a particular element. The isotope effect is a consequence of the Heisenberg uncertainty principle on 75 levels of the energy distribution of molecular vibrations (Metallomics, 2016, Accepted Manuscript DOI: 10.1039 / C6MT00148C). It is known that the isotopic weight has an effect on the value of the effective radius of electron orbits of atoms and leads to changes in the characteristics of the fine structure of atomic energy levels. Biochemical processes of organisms are highly dependent on the conditions of their occurrence, usually using resonant effects, so the slightest deformations of electron orbitals can lead to disruption of biochemical reactions.
A number of studies have demonstrated that the isotopic composition of tissues and organs can serve as a diagnostic marker. In particular, the study of correlations of Cu and Zn isotopes in blood showed their promising relationship to age, sex and pathologies. For example, assessment of the ratio of Cu isotopes in the blood serum is a new approach to the diagnosis and prognosis of liver cirrhosis (see M. Costas-Rodriguez et al., Isotopic analysis of Cu in blood serum by multi-collector ICP-mass spectrometry: a new approach for the diagnosis and prognosis of liver cirrhosis? Metallomics 7: 491-498 (2015)), and the isotopic composition of Zn in breast tissue makes it possible to diagnose cancer (F. Lamer et al., Zinc isotopic compositions of breast cancer tissue, Metallomics 7: 107-112 (2015)).
In particular, it was found that natural water and most foods that are used by humans contain heavy isotopes of chemical elements. Every human, being a complex biochemical system, fractionates heavy isotopes during his lifetime. As a result, heavy isotopes, which accumulate in the human organism starting at birth, gradually "integrate" into the cells.
While not wishing to be bound by theory, the present inventors believe that each of hydrogen, carbon, oxygen, nitrogen potassium, magnesium, zinc, rubidium, silicon, iron, molybdenum, selenium, nickel, germanium, chromium, copper, and vanadium play important roles in autocatalytic reactions in the body of an animal, such as a human or other mammal. The products of such autocatalytic reactions, such as proteins, play important chemical and structural roles in the body, including immune function. Fully functional products of such reactions require a specific, "correct" chirality at various chiral centers within the product. The inventors further understand that heavy isotopes accumulate in the body beginning at birth such that, over time, the relative abundance of each element's isotopes drifts further and further from the naturally occurring relative abundance, becoming increasingly over-weighted with respect to heavy isotopes. Heavy isotopes can affect autocatalytic reactions by reducing the proportion of products that have the "correct" chirality. See, e.g., Tsuneomi Kawasaki et al., Asymmetric Autocatalysis Triggered by Carbon Isotope (13C/12C) Chirality, Science 324: 492-95 (2009). This causes a reduction in the proportion of products of autocatalytic reactions that are fully functional. In sum, the cumulative divergence of the body's isotope relative abundances from the natural relative abundance causes a decrease in the functionality of various proteins and other molecules in the body, leading to a decline in health with age.
The present inventors believe such a decline can be countered by restoring the body's original isotope relative abundances, or by moving the isotope relative abundances in that direction. Similarly, pathogenic infectious bacteria can be suppressed by treating them with light isotopes of the elements listed above, which can alter the chirality of the autocatalytic products of such bacteria, resulting in their death or suppressed growth. Thus, treatment with light isotopes can have the dual result of improving the body's ability to fight off a bacterial infection and simultaneously killing or suppressing the growth of infective bacteria. Further, the quantity of light isotope that is effective may be proportional to the quantity of the corresponding element that is present in the body. Where the body contains a relatively large quantity of the element, a correspondingly relatively large amount of the element's light isotope will be required to provide an effective dosage amount. On the other hand, where the body contains a relatively small quantity of the element, a correspondingly relatively small amount of the element's light isotope will be required to provide an effective dosage amount.
Light isotopes have been used in medicine, veterinary medicine, food industry and agriculture without producing adverse effects on organisms.
Patent RU2498807 purports to disclose a new treatment of acute radiation sickness which uses water with light isotopes as a therapeutic agent. The remedy is said to improve survival and accelerate recovery of hematopoiesis and body weight.
International publication no. WO 01/82871 describes a method of diagnosis and treatment of colon cancer. This method uses zinc and the unstable isotope 62Zn in the form of zinc acetate, zinc chloride and zinc sulfate, as well as the phosphate carrier.
According to U.S. publication no. 2016/0151415, a pharmaceutical composition for improving health condition and treatment of pathologies and degenerative diseases includes a pharmaceutically acceptable carrier and an active isotope selective ingredient that includes at least one chemical element wherein the isotope distribution is different from that occurring in nature, inherent in such chemical element. Thus 39K, 24Mg, 64Zn, 85Rb, 26Si, 40Ca, 63Cu, 54Fe, 52Cr, 58Ni, 92Mo, 107Ag, 79Br, 35Cl and combinations thereof are used as possible selective isotopes. However, the antibacterial effect of the above isotopes is not described in the said application.
Publication No. GB2531207 purports to disclose an antibacterial agent which consists of at least one of the isotopes of hydrogen selected from the group including 1H, 2H, 3H, 4H, 5H, 6H and 7H, a hydrogen molecule (H2), metal hydride, a hydrogen ion (H30 ), a hydride ion (H−) and atomic hydrogen. The composition described in this publication is said to exhibit antibacterial activity and reduce propagation of drug-resistant microorganisms. In addition, hydrogen, after its exposure to pathogenic microorganisms, combines with oxygen to form water. According to the publication, this eliminates adverse effects of the antibacterial agent on the organism to which it is administered, and the said agent has little effect on the host organism even if it is administered in combination with another drug(s).
There remains a need for new, effective antibacterial compositions.

Antibacterial composition and its use in treating bacterial infections


The present inventions relates to nucleus-extended perylenebisimides of formula (I)

The present invention relates to nucleus-extended perylenebisimides of general formulae (I) and (II)
wherein
R1 and R2 are each independently of the other unsubstituted or substituted C1-C24alkyl, C1-C24cycloalkyl, or C6-C10aryl, and
A1 and A3 are each independently of the other xe2x80x94Sxe2x80x94, xe2x80x94Sxe2x80x94Sxe2x80x94, xe2x80x94CHxe2x95x90CHxe2x80x94, R3OOCxe2x80x94C(xe2x80x94)xe2x95x90C(xe2x80x94)xe2x80x94COOR3, xe2x80x94Nxe2x95x90Nxe2x80x94 or xe2x80x94N(R4)xe2x80x94, or a linkage selected from the group consisting of the organic radicals of formulae (III), (IV), (V), (VI) and (VII)
wherein
R3 is hydrogen, C1-C24alkyl or C1-C24cycloalkyl,
R4 is unsubstituted or substituted C1-C24alkyl, C1-C24cycloalkyl, phenyl, benzyl, xe2x80x94COxe2x80x94C1xe2x80x94C4alkyl, xe2x80x94COxe2x80x94C6H5 or C1-C4alkylcarboxylic acid (C1-C4alkyl) ester, and
A2 is a linkage of formula (III), (IV) or (V),
also to intermediates for the preparation of compounds (I) and (II) and to processes for the preparation of those intermediates and also to processes for the preparation of compounds (I) and (II), and to the use thereof as colourants.
Perylenes, as is known (see Heterocycles, Vol. 40, No. 1, (1995) 477-500), are photostable fluorescent dyes that are often distinguished by high fluorescence quantum yields. A disadvantage thereof is, however, that perylenes have a low degree of solubility in aqueous media.
Chem. Ztg. (1975), 99, 92-93 describes, inter alia, nucleus-extended perylenes that are obtainable by Diels-Alder reaction of 4-phenyl-1,2,4-triazoline-3,5-dione with perylene and that may exhibit absorptions at 600 nm.
Further Diels-Alder reactions on perylenes are described in Heterocycles, Vol. 40, No. 1, 1995. J. Org. Chem. USSR, (1986), 22, 943-946 describes the preparation of thio- and dithio-cyclic derivatives of perylene-3,4,9,10-tetracarboxylic acid. Furthermore, J. Org. Chem. USSR, (1980), 16, 762-7 describes a process for the preparation of nitrogen-cyclic derivatives of perylene-3,4,9,10-tetracarboxylic acid.
The problem underlying the invention was accordingly to provide further nucleus-extended perylenes, especially nucleus-extended perylenebisimides, that preferably as fluorescent dyes have good fastness to heat and to light; perylenes suitable as NIR dyes or as fluorescent markers were also to be provided.
Accordingly, there have been found the nucleus-extended perylenebisimides of general formulae (I) and (II) defined at the beginning.
C1-C24Alkyl is, for example, methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, n- or neo-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, heneicosyl, docosyl or tetracosl, preferably 1-(C1-C9alkyl)-C2-C10alkyl, such as 1-methyl-ethyl, 1-ethyl-n-propyl, 1-n-propyl-n-butyl, 1-n-butyl-n-pentyl, 1-n-hexyl-1-n-heptyl, 1-n-heptyl-1-n-octyl, 1-n-octyl-1-n-nonyl or 1-n-nonyl-1-n-decyl, or C1-C8alkyl, such as methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, n- or neo-pentyl, n-hexyl, n-heptyl or n-octyl and especially C1 -C4alkyl, such as methyl, ethyl, n- or iso-propyl or n-, iso-, sec- or tert-butyl.
C3-C14Cycloalkyl is, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl or cyclotetradecyl, preferably C5-C8cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
Especially preferred compounds of formulae (I) and (II) are those wherein R1 and/or R2 denote a secondary alkyl radical, such as 1-(C1-C9alkyl)-C2-C10alkyl, especially those wherein the radical R1has a so-called xe2x80x9cswallowtail structurexe2x80x9d, such as 1-methyl-ethyl, 1-ethyl-n-propyl, 1-n-propyl-n-butyl, 1-n-butyl-n-pentyl, 1-n-hexyl-1-heptyl, 1-n-heptyl-1-n-octyl, 1-n-octyl-1-n-nonyl, 1-n-nonyl-1-decyl, or an aromatic radical, especially the phenyl radical, very especially C1-C6alkyl-substituted phenyl, such as 2,6-di-tert-butylphenyl and 2,5-di-tert-butylphenyl.
C6-C10Aryl is, for example, phenyl or 1- or 2-naphthyl, especially phenyl.
xe2x80x94COxe2x80x94C1-C4Alkyl is xe2x80x94CO-methyl, xe2x80x94CO-ethyl, xe2x80x94CO-n-propyl, xe2x80x94CO-isopropyl, or xe2x80x94CO-n-, xe2x80x94CO-iso-, xe2x80x94CO-sec- or xe2x80x94CO-tert-butyl.
C1-C4Alkylcarboxylic acid (C1-C4alkyl) ester is, for example, methylcarboxylic acid methyl ester, methylcarboxylic acid ethyl ester, methylcarboxylic acid n-propyl ester, methylcarboxylic acid isopropyl ester, methylcarboxylic acid n-butyl ester or methylcarboxylic acid isobutyl ester, methylcarboxylic acid sec-butyl ester or methylcarboxylic acid tert-butyl ester or ethylcarboxylic acid methyl ester, ethylcarboxylic acid ethyl ester, ethylcarboxylic acid n-propyl ester, ethylcarboxylic acid isopropyl ester, ethylcarboxylic acid n-butyl ester, ethylcarboxylic acid sec-butyl ester or ethylcarboxylic acid tert-butyl ester, n-propylcarboxylic acid methyl ester or n-butylcarboxylic acid methyl ester.
Hal is, for example, halide and denotes fluoride, chloride, bromide or iodide.
Especially preferred perylene-3,4:9,10-tetracarboxylic acid bisimides of general formulae (I) and (II) are those wherein R1 and R2 are each independently of the other 1-n-hexyl-1-heptyl, 2,5-di-tert-butylphenyl, 1-nonyl-1-decyl or 1-n-butyl-n-pentyl; very especially R2 is R1.
Very special preference is given to perylene-3,4:9,10-tetracarboxylic acid bisimides of general formulae (I) and (II) wherein A1 is xe2x80x94Sxe2x80x94, NR4, xe2x80x94CHxe2x95x90CHxe2x80x94, R3OOCxe2x80x94C(xe2x88x92) xe2x95x90C(xe2x88x92)xe2x80x94COOR3, or a linkage of formula (III), (IV), (V), (VI) or (VII) and A2 and A3 are an organic radical of formula (V) or A2 and A3 are each independently of the other an organic radical of formula (III), (IV) or (V).
Preferred perylenes of the present invention are the compounds of formulae (VIII) to (XX) given below, wherein R1 and R2 are especially each independently of the other 1-hexyl-1-heptyl, 2,5-di-tert-butylphenyl, 1-nonyl-1-decyl or 1-butyl-pentyl,
very especially R1 and R2 in (VII) are 1-n-hexyl-1-heptyl, 2,5-di-tert-butylphenyl or 1-butylpentyl, and
wherein very especially R1 and R 2 are 1-n-hexyl-1-heptyl, and
wherein preferably
R4 is unsubstituted or substituted C1-C24alkyl, C1-C24cycloalkyl, phenyl, and especially cyclohexyl or 2,5-di-tert-butylphenyl, and
R1 and R2 are very especially 1-n-hexyl-1-heptyl, and
wherein
R1 and R2 are very especially 1-n-hexyl-1-heptyl, and
wherein
R1 and R2 are very especially 1-n-hexyl-1-heptyl, and
wherein
R1 and R2 are very especially 1-n-hexyl-1-heptyl, 2,5-di-tert-butylphenyl or 1-n-butyl-n-pentyl, and
wherein preferably
R4 is unsubstituted or substituted C1-C24alkyl, phenyl, benzyl, xe2x80x94COxe2x80x94C1-C4alkyl, xe2x80x94COxe2x80x94C6H5 or C1-C4alkylcarboxylic acid (C1-C4alkyl) ester, and especially C1-C4alkyl, more especially methyl, benzyl, xe2x80x94CH2COOC2H5, xe2x80x94COCH3 or xe2x80x94CO-phenyl, and
R1 and R2 are very especially 1-n-hexyl-1-heptyl, 2,5-di-tert-butylphenyl or 1-n-butyl-n-pentyl, and
wherein
R1 and R2 are very especially 1-n-hexyl-1-heptyl, 2,5-di-tert-butylphenyl or 1-n-butyl-n-pentyl, and
wherein
R1 and R2 are very especially 1-n-hexyl-1-heptyl, 2,5-di-tert-butylphenyl or 1-n-butyl-n-pentyl, and
wherein especially
R4 is substituted or unsubstituted phenyl, and
R1 and R2 are very especially 1-n-hexyl-1-heptyl, and
wherein preferably
R3 is C1-C4alkyl, especially methyl or ethyl, and
R1 and R2 are very especially 1-n-hexyl-1-heptyl, and
wherein
R1 and R2 are very especially 1-n-hexyl-1-heptyl, and
wherein especially
R4 is phenyl, and
R1 and R2 are very especially 1-n-hexyl-1-heptyl, and
wherein especially
R4 is phenyl, and
R1 and R2 are very especially 1-n-hexyl-1-heptyl.
The perylenebisimides (I) according to the invention wherein A1 is A4, wherein A4 is a linkage selected from the group consisting of the organic radicals of formulae (III), (IV), (V) and (VII), and perylenebisimides (II) wherein A2 is A5, wherein A5 is a linkage of formula (III) or (V), and A1 is A6, wherein A6 is a linkage of formula (V), are preferably obtained by Diels-Alder reactions, as described in J.Chem.Soc. (1957), 96, 5616-4619.
The present invention accordingly relates also to a process for the preparation of perylenebisimides (I) wherein A1 is A4, wherein A4 is a linkage selected from the group consisting of the organic radicals of formulae (III), (IV), (V), (VII) and xe2x80x94Nxe2x95x90Nxe2x80x94, by Diels-Alder reaction of a diene with a dienophile at elevated temperature, wherein there are reacted, as diene, a perylenebisimide of formula (XXI)
and, as dienophile, a compound selected from the group consisting of the compounds of formulae (XXII), (XXIII) and (XXIV)
The order in which the starting materials (XXI) and (XXII), (XXI) and (XXIIa), or (XXI) and (XXIII), or (XXI) and (XXIV), are added is not generally important. It has, however, proved to be advantageous to use a compound of formula (XXII), (XXIIa), (XXIII) or (XXIV) as the initial charge and then to add the compound (XXI).
The compounds of formulae (XXII), (XXIIa), (XXIII) and (XXIV) are generally used in excess, preferably in a molar ratio of compounds (XXII):(XXI), (XXIIa):(XXI), (XXIII):(XXI) or (XXIV):(XXI) in the range of from 1.1:1 to 20:1, especially from 1.3:1 to 15:1.
The reaction is preferably carried out at a reaction temperatures in the range of from 80 to 200xc2x0 C., especially from 100 to 150xc2x0 C. According to observations hitherto, the success of the reaction is not dependent upon the pressure range selected. For simplicity""s sake, the reaction is customarily carried out at atmospheric pressure, but it is also possible to select pressures in the range of from 10 kPa to 10 MPa. The reaction times are selected, depending on the reaction temperature chosen, preferably in the range of from 1 hour to 4 weeks, especially in the range of from one day to 4 weeks.
It has proved advantageous to carry out the reaction in the presence of an organic solvent. As solvent there come into consideration, for example, dipolar aprotic solvents, such as acetonitrile, benzonitrile, N,Nxe2x80x2-dimethylformamide, N,Nxe2x80x2-dimethylacetamide, nitrobenzene, N-methylpyrrolidone, aliphatic hydrocarbons, which may if desired be halogenated, such as trichloroethane, dichloroethane, trichloromethane or dichloromethane, or cycloalkanes, such as cyclohexane or cycloheptane, or aromatic hydrocarbons or mixtures thereof, such as benzine (as a mixture of different, essentially aliphatic hydrocarbons), or unsubstituted or alkyl-, alkoxy- or halo-substituted benzene, such as toluene, xylene, anisole or chlorobenzene, and also ethers, such as tetrahydrofuran, dioxane or EtOCH2CH2OH (e.g. in the form of Cellosolve(copyright) commercially available from Fluka) or glycol ethers, such as ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether, or nitrogen-containing solvents, such as pyridine, triethylamine, picoline or quinoline, and keto-group-containing solvents, such as acetone or methyl ethyl ketone. The above-mentioned solvents may also be used in the form of mixtures with one another.
The weight ratio of solvent to the sum of the reactants is customarily in the range of from 0.001 to 20% by weight, preferably from 0.001 to 10% by weight.
In an especially preferred embodiment of the process according to the invention, a compound of formula (XXII), (XXIIa), (XXIII) or (XXIV), preferably of formula (XXII), is reacted with a compound (XXI).
In a further preferred embodiment, the reaction is carried out in a protective gas atmosphere. Preferred protective gases are, for example, nitrogen and the noble gases, such as helium or argon.
It has also proved to be extremely advantageous to carry out the process according to the invention in the presence of an oxidising agent, for example para-chloranil, in order to rearomatise the addition product.
The perylenebisimides of formula (XXI) are known or can be prepared according to known methods as described in Heterocycles (1995), 40, 477-500, for example by reacting a perylenebisanhydride with a primary amine to form a perylenebisimide.
The present invention relates also to a process for the preparation of perylenebisimides (II) wherein A2 is an organic radical of formula (III), (IV) or (V) and A1 is (V), by Diels-Alder reaction of a diene with a dienophile at elevated temperature, wherein a perylenebisimide of formula (XXI) is reacted with a compound of formula (XXII), (XXIIa), (XXIII), or (XXIV), or perylenebisimides of formula (XVI) are reacted with compounds of formula (XXII), (XXIIa) or (XXIII).
The reaction parameters generally correspond to those in the Diels-Alder reaction described above.
The compounds of formulae (XXII), (XXIIa), (XXIII) and (XXIV) are generally used in excess, preferably in a molar ratio of the compounds ((XXII) or (XXIIa) or (XXIII) or XXIV)):((XXI) or (XVI)) in a range of from 2.1:1 to 50:1, especially from 1.3:1 to 15:1.
The order in which the starting materials (XXI), (XXII), (XXIIa), (XXIII) or (XXIV) are added is generally not important. It has, however, proved advantageous to use the compound of formula (XXI) as the initial charge and then to add the compounds (XXII), (XXIIa), (XXIII) or (XXIV).
The perylenebisimides (I) and (II) prepared according to the Diels-Alder reactions according to the invention can be purified and isolated in accordance with customary methods, such as by chromatography, especially column chromatography, or crystallisation, especially extractive recrystallisation (e.g. analogously to the method described in Chem. Ber. 118 (1985) 4641-4645)).
Generally the perylenebisimides (I) and (II) can be used after purification and isolation directly for further reactions.
The present invention accordingly relates also to a process for the preparation of perylenebisimides of formula (IXa), (IXb) or (X), wherein the compound of formula (VII) is reacted with
a) NH3 or amidosulfuric acid, or
b) a primary amine of formula (XXV) H2Nxe2x80x94R4, or
c) a primary diamine of formula (XXVI)
The amine (XXV) or (XXVI) or NH3 or amidosulfuric acid is generally used in excess, preferably in a molar ratio of the perylenebisimide (I) to (XXV) or (XXVI) or NH3 or amidosulfuric acid in a range of from 1:1.1 to 1:20, especially in the range of from 1:1.3 to 1:15.
The reaction is preferably carried out at reaction temperatures in the range of from 80 to 200xc2x0 C. According to observations hitherto, the success of the reaction is not dependent upon the pressure range selected. For simplicity""s sake, the reaction is customarily carried out at atmospheric pressure, but it is also possible to select pressures in the range of from 10 kPa to 10 MPa. The reaction times are selected, depending on the reaction temperature chosen, preferably in the range of from 1 hour to 40 hours, especially in the range of from 2 hours to 25 hours.
It has proved advantageous to carry out the reaction in the presence of an organic solvent. As solvent there come into consideration, for example, those mentioned above. Special preference is given to nitrogen-containing solvents, especially quinoline, and halogenated aliphatic hydrocarbons, such as trichloromethane.
The weight ratio of the sum of the reactants to the solvent is customarily in the range of from 100 to 0.001% by weight, preferably from 50:0.001% by weight.
A preferred embodiment of the process according to the invention relates to the reaction in the presence of N,Nxe2x80x2-dicyclohexylcarbodiimide (DCC) in trichloromethane.
An especially preferred embodiment of the process according to the invention relates to the reaction in the presence of N,Nxe2x80x2-dicyclohexylcarbodiimide (DCC) and trifluoroacetic acid in trichloromethane.
The molar ratio of DCC to the compound (VII) is customarily in the range of from 20:1 to 1:1, preferably from 15:1 to 1:1 and very especially in the range of from 10:1 to 1:1.
The molar ratio of trifluoroacetic acid to the compound (VIII) is customarily in the range of from 0.0001:100 to 0.1:10.
In a preferred embodiment, the reaction is carried out in a protective gas atmosphere. Preferred protective gases are, for example, nitrogen and the noble gases, such as helium or argon.
It has also been found that the compound (VII) can be converted into a dicarboxylic acid derivative (XXVIIa)
and by esterification into the dicarboxylic acid ester of formula (XXVIIb)
wherein R5 is C1-C24alkyl or C1-C24cycloalkyl.
A further embodiment of the present invention accordingly relates also to a process for the preparation of compounds of formula (XXVIIa) by hydrolysis of an anhydride, wherein the compound (VIII) is used as anhydride and is reacted with an acid or a base, preferably in an aqueous medium.
The hydrolysis of anhydrides is known and is described, for example, in Survey of Organic Syntheses, by Calvin A. Buehler and Donald E. Pearson, Wiley-Interscience, USA, (1970).
The reaction is preferably carried out at reaction temperatures in the range of from xe2x88x9210 to 200xc2x0 C., especially from 0 to 150xc2x0 C. According to observations hitherto, the success of the reaction is not dependent on the pressure range selected. For simplicity""s sake, the reaction is customarily carried out at atmospheric pressure, but it is also possible to select pressures in the range of from 10 kPa to 10 MPa. The reaction times are selected, depending on the reaction temperature chosen, preferably in the range of from 1 hour to 24 hours.
As acid there may be used, for example, an inorganic acid, such as hydrochloric acid, sulfuric acid, Lewis acids, such as boron trifluoride, or organic acids, such as methanesulfonic acids, formic acid or para-toluenesulfonic acid.
As bases there may be used, for example, alkali metal alcoholates, such as sodium or potassium methanolate or sodium or potassium ethanolate, and alkali metal carbonates and alkali metal hydrogen carbonates, such as sodium carbonate or potassium carbonate, and sodium hydrogen carbonate or potassium hydrogen carbonate, and alkali metal hydroxides, such as sodium hydroxide, potassium hydroxide, especially potassium hydroxide powder (85% by weight potassium hydroxide and 15% by weight water), and also lithium aluminium hydride, potassium tert-butanolate, triethylamine, aluminium alkanolate and also non-nucleophilic bases, such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene ((DBN) or N,N,Nxe2x80x2,Nxe2x80x2-tetramethylethylenediamine (TMEDA).
The acid or base is generally used in a molar ratio of acid or base to compound (VIII) in the range of from 0.1:1 to 20:1.
It has proved advantageous to carry out the reaction in the presence of an organic solvent. As solvent there come into consideration, for example, those mentioned above.
The weight ratio of the sum of the reactants to the solvent is customarily in the range of from 0.001 to 20% by weight, preferably from 0.001 to 10% by weight.
In a further preferred embodiment, the reaction is carried out in a protective gas atmosphere. Preferred protective gases are, for example, nitrogen and the noble gases, such as helium or argon.
The present invention relates also to a process for the preparation of diester derivatives (XXVIIb) by esterification of a dicarboxylic acid, wherein a compound of formula (XXVIIa) is reacted with an alcohol of formula (XXVIII), HO-R5, or with an alkyl halide of formula (XXIX), Hal-R5, in the presence of an acid or a base.
Suitable bases and acids are those mentioned above.
Methods for the esterification of carboxylic acids are known and described, for example, in Survey of Organic Synthesis, (1970).
A particular embodiment of the process according to the invention relates to the reaction with a base. Non-nucleophilic bases in particular have proved to be advantageous.
Generally the molar ratio of base to compound (XVIIa) is in the range of from 100:1 to 1:100, preferably in the range of from 20:1 to 1:20.
The molar ratio of alkyl halide to base is generally in the range of from 5:1 to 1:5, preferably in the range of from 2:1 to 1:2.
It has proved advantageous to carry out the reaction according to the invention in the presence of solvents. Suitable solvents are those mentioned above.
Generally the solvent is used in an amount sufficient to dissolve the compound (XVIIa).
It has also been found that the dicarboxylic acid derivatives (XVIIa) and anhydrides of formula (VII) can be decarboxylated.
The present invention accordingly relates also to a process for the preparation of perylenebisimides of formula (XI), by decarboxylation of a dicarboxylic acid or an anhydride with copper or a copper-containing compound, wherein a compound of formula (XXVIIa) or (VIII) is reacted in the presence of a solvent.
The decarboxylation of carboxylic acids can, as is known, be carried out with copper in the presence of quinoline (see Survey of Organic Synthesis, (1970), 144, 145 ).
Copper denotes, for example, copper powder, and as copper-containing compound there can be used copper(I) or copper(II) salts, preferably copper(I) or copper(II) oxide, copper chromite or copper sulfate; it is preferred to use copper powder.
Copper or a copper-containing compound is generally used in excess. The molar ratio of copper (or copper equivalent in copper-containing compounds) to the compound of formula (XVIIa) or (VIII) is preferably in the range of from 1.1:1 to 20:1, especially in the range of from 1.3:1 to 15:1.
The reaction is preferably carried out at reaction temperatures in the range of from 80 to 200xc2x0 C., especially from 120 to 180xc2x0 C. According to observations hitherto, the success of the reaction is not dependent on the pressure range selected. For simplicity""s sake, the reaction is customarily carried out at atmospheric pressure, but it is also possible to select pressures in the range of from 10 kPa to 10 MPa. The reaction times are selected, depending on the reaction temperature chosen, preferably in the range of from 1 hour to 48 hours, especially in the range of from 1 hour to 10 hours.
It has proved advantageous to carry out the reaction in the presence of an organic solvent. As solvent there come into consideration, for example, those mentioned above for the process for the preparation of the compound of formula (VII). Especially preferred solvents are nitrogen-containing solvents, with special preference being given to quinoline and 3-picoline.
The weight ratio of the sum of the reactants to the solvent is customarily in the range of from 0.001 to 20% by weight, preferably from 0.001 to 10% by weight.
In a further preferred embodiment, the reaction is carried out in a protective gas atmosphere. Preferred protective gases are, for example, nitrogen and the noble gases, such as helium or argon.
The present invention relates also to perylenebisimides of formula (XXX) and to perylene monoanhydride-monoimides of formula (XXXI)
wherein
R7 and R8 are each independently of the other hydrogen, NO2, PO(OR11)(OR12), Br, NH2 or N(R11R2)2, wherein
R11 and R12 are each independently of the other a radical mentioned under R2, and R9 and R10 are each independently of the other hydrogen, NO2, NH2 or N(R11R2)2.
Special preference is given to substituted perylenebisimides of formulae (XXXII) to (XXXIX), wherein especially R1 and R2 are each independently of the other 1-n-hexyl-1-heptyl, 2,5-di-tert-butylphenyl, 1-nonyl-1-decyl or 1-n-butyl-n-pentyl,
and wherein preferably
R12 and R11 are unsubstituted or substituted C1-C4alkyl, especially methyl or ethyl, and wherein R1 and R2 are very especially 1-hexyl-1-heptyl or 1-butyl-pentyl, and
and
wherein R1 and R2 are very especially 1-hexyl-1-heptyl, 2,5-di-tert-butylphenyl or 1-butylpentyl, and
and
wherein R1 and R2 are very especially 1-hexyl-1-heptyl, and
wherein R1 and R2 are very especially 1-hexyl-1-heptyl or 1-butyl-pentyl, and
wherein R1 and R 2 are very especially 1-hexyl-1-heptyl or 1-butyl-pentyl, and
wherein preferably
R11 and R3 are unsubstituted or substituted C1-C4alkyl, especially methyl or ethyl, and
wherein R1 is very especially 1-hexyl-1-heptyl or 1-butyl-pentyl, and
wherein R1 is very especially 1-hexyl-1-heptyl or 1-butyl-pentyl.
Perylene monoanhydride-monoimides can be used as starting compounds in the preparation of perylenebisimides in close analogy to known methods. For example, Heterocycles (1995), 40, 477-500 describes how anhydride derivatives of perylenes can be reacted with primary amines to form the corresponding imides.
The anhydride derivatives according to the invention can also be used as fluorescent markers.
The nitro derivatives, especially monosubstituted derivatives, of derivatives of perylenetetracarboxylic acid have hitherto been obtainable only in unsatisfactory yields (see, for example, J. Org. Chem. USSR (Engl. Translation) 1980, 16, 762-766).
It has now been found that perylenebisimides of formula (XXI) and perylene monoanhydride-monoimides of formula (XXXI) wherein R9 and R10 are hydrogen can be substituted by a single nitro group in good yields.
The present invention accordingly relates also to a process for the preparation of compounds of formulae (XXXIII), (XXXVIII) and (XXXIX), wherein compounds of formula (XXI) or (XXXI) wherein R9 and R10 are hydrogen are reacted with N2O4 in the presence of a solvent.
The reaction is preferably carried out at reaction temperatures in the range of from xe2x88x9210 to 40xc2x0 C., especially from 0 to 25xc2x0 C. According to observations hitherto, the success of the reaction is not dependent on the pressure range selected. For simplicity""s sake, the reaction is customarily carried out at atmospheric pressure, but it is also possible to select pressures in the range of from 10 kPa to 10 MPa. The reaction times are selected, depending on the reaction temperature chosen, preferably in the range of from 1 hour to 24 hours, especially in the range of from 2 hours to 10 hours.
The molar ratio of N2O4 to the compounds of formula (XXI) is customarily in the range of from 0.5:1 to 2:1, preferably from 0.8:1 to 1.5:1.
The molar ratio of N2O4 to the compounds of formula (XXXI) wherein R9 and R10 are hydrogen is customarily in the range of from 0.5:1 to 4:1, preferably from 0.8:1 to 1.5:1.
It has proved advantageous to carry out the reaction in the presence of an organic solvent. As solvents there come into consideration, for example, those solvents mentioned above for the process for the preparation of perylenebisimides (I) wherein A1 is A4. Especially preferred solvents are halogenated aliphatic hydrocarbons, such as especially dichloromethane.
A particular embodiment of the process according to the invention relates to the reaction in the presence of a catalyst.
As catalyst there are used, for example, acids, such as sulfonic acids, trifluoroacetic acid, trifluoromethanesulfonic acid, methanesulfonic acid or toluenesulfonic acid, preferably methanesulfonic acid.
The molar ratio of catalyst to the compound of formula (XXI) or (XXXI) wherein R9 and R10 are hydrogen is customarily in the range of from 0.0001:1 to 1:1.
The molar ratio of solvent to the compound of formula (XXI) or (XXXI) wherein R9 and R10 are hydrogen is generally in the range of from 0.01:1 to 100:1, preferably from 0.1:1 to 50:1.
In a further preferred embodiment, the reaction is carried out in a protective gas atmosphere. Preferred protective gases are, for example, nitrogen and the noble gases, such as helium or argon.
The compounds (XXXIII), (XXXVIII) and (XXXIX) prepared according to the nitration processes according to the invention can be purified and isolated according to customary methods, such as by chromatography, especially column chromatography, or crystallisation, especially extractive recrystallisation.
It has also been found that the nitro derivatives of formulae (XXXIII), (XXXVIII) and (XXXIX) can be converted to their amino derivatives by reduction.
The present invention accordingly relates also to a process for the preparation of compounds of formulae (XXXVa), (XXXVIa) and (XXXVIIa) wherein perylenebisimides of formulae (XXXIII), (XXXVIII) and (XXXIX) are reacted
a) with iron in the presence of an acid, or
b) with palladium in the presence of hydride transporters such as triethylamine/formic acid or triethylammonium formate, hydrazine or derivatives thereof, or phosphinic or phosphoric acid.
For example, it is known from Survey of Organic Syntheses, by Calvin A. Buehler and Donald E. Pearson, Wiley-Interscience, USA, (1970), 413 to 417, that nitro compounds can be reduced with iron under acid conditions or with palladium/carbon and hydrogen. Furthermore, reduction with palladium is described, in the presence of formic acid, in J. Chem. Soc. Perkin Trans,I, (1977), 443, and in the presence of triethylammonium formate, in J.Org.Chem.(1977), 42,3491.
The reaction is preferably carried out at reaction temperatures in the range of from xe2x88x9210 to 150xc2x0 C., especially from 0 to 100xc2x0 C. According to observations hitherto, the success of the reaction is not dependent upon the pressure range selected. For simplicity""s sake, the reaction is customarily carried out at atmospheric pressure, but it is also possible to select pressures in the range of from 10 kPa to 10 MPa. The reaction times are selected, depending on the reaction temperature chosen, preferably in the range of from 5 minutes to 24 hours, especially in the range of from 5 minutes to 5 hours, very especially from 5 minutes to 2 hours.
As acid there is customarily used an inorganic or organic acid. Preference is generally given to the use of an inorganic acid, for example hydrochloric acid, especially concentrated hydrochloric acid.
The molar ratio of iron to (XXXIII), (XXXVIII) and (XXXIX) is customarily in the range of from 1:10 to 15:1, preferably from 1:1 to 10:1.
The weight ratio of acid to iron is generally in the range of from 0.001:1 to 100:1.
It has proved advantageous to carry out the reaction in the presence of an organic solvent. As solvent there come into consideration, for example, those listed above for the process for the preparation of perylenebisimides (I) wherein A1 is A4.
The weight ratio of (XXXIII), (XXXVIII) or (XXXIX) to the solvent used is customarily in the range of from 0.001 to 100% by weight, preferably from 0.001 to 20% by weight.
In a preferred embodiment of the process according to the invention, it has proved advantageous to use palladium/carbon instead of palladium.
The weight ratio of palladium/carbon (with 5% by weight palladium based on carbon) to (XXXIII), (XXXVIII) and (XXXIX) is generally in the range of from 0.01:1 to 1:1, preferably in the range of from 0.1:1 to 0.5:1 and very especially in the range of from 0.1:1 to 0.3:1.
The molar ratio of triethylamine to formic acid is customarily in the range of from 1:0.1 to 0.9:1, preferably in the region of 1:0.5 and especially in the region of 1:0.7.
The molar ratio of triethylamine or triethylammonium formate to (XXXIII), (XXXVIII) and (XXXIX) is customarily in the range of from 5:1 to 100:1.
In a further preferred embodiment, the reaction is carried out in a protective gas atmosphere. Preferred protective gases are, for example, nitrogen and the noble gases, such as helium or argon.
The amino derivatives (XLII) and (XLIII) prepared according to the processes of the invention can be purified and isolated in accordance with customary methods, such as by chromatography, especially column chromatography, or crystallisation, especially extractive recrystallisation.
The present invention relates also to a process for the preparation of compounds of formulae (XXXV), (XXXVI) and (XXXVII), wherein the compounds of formula (XXXVa) or (XXXVla) and (XXXVIIa) are reacted with a base with alkyl halides of formula R""11-Hal and/or R3-Hal, wherein Hal is fluoride, chloride, bromide, iodide and R11 and R3 are each independently of the other hydrogen or C1-C24alkyl, C1-C24cycloalkyl, and R11 and R3 are preferably the same. Houben-Weyl, Methoden der Organischen Chemie, G. Thieme Verlag Stuttgart, 1957, 4th ed., Vol. 11, Pt, 1., Chap. 2 describes methods for alkylating amines.
The reaction is preferably carried out at reaction temperatures in the range of from xe2x88x9210 to 150xc2x0 C., especially from 0 to 50xc2x0 C., very especially from 0 to 30xc2x0 C. According to observations hitherto, the success of the reaction is not dependent on the pressure range selected. For simplicity""s sake, the reaction is customarily carried out at atmospheric pressure, but it is also possible to select pressures in the range of from 10 kPa to 10 MPa. The reaction times are selected, depending on the reaction temperature chosen, preferably in the range of from 1 hour to 48 hours.
As base there is customarily used an inorganic base, such as, for example, an alkali metal hydroxide, such as potassium hydroxide, sodium hydroxide, or an alkali metal carbonate, such as sodium carbonate, potassium carbonate, or an alkali metal hydrogen carbonate, such as sodium hydrogen carbonate or potassium hydrogen carbonate. It has proved especially advantageous to use aqueous potassium hydroxide. The weight ratio of potassium hydroxide to water is generally in the range of from 0.0001:1 to 1:1.
The molar ratio of the base to the amino derivatives of formula (XXXVa) or (XXXVla) and (XXXVIIa) is customarily in the range of from 1:10 to 10:1, preferably from 1:5 to 5:1.
The molar ratio of R11-Hal to R3-Hal is generally in the range of from 1:100 to 100:1.
It has proved advantageous to carry out the reaction in the presence of an organic solvent. As solvent there come into consideration, for example, those solvents listed above in the process for the preparation of perylenebisimides (I) wherein A1 is A4.
The weight ratio of the sum of the reactants to the solvent is customarily in the range of from 0.001 to 100% by weight, preferably from 0.001 to 20% by weight.
A special development of the present reaction relates to the use of dipolar aprotic solvents.
It has proved especially advantageous to carry out the reaction in the presence of a dipolar aprotic solvent and a phase-transfer catalyst.
As phase-transfer catalyst there may be used, for example, triethylbenzylammonium chloride or triethylbenzylammonium bromide.
The molar ratio of phase-transfer catalyst to (XXXVa) or (XXXVIa) and (XXXVIIa) is customarily in the range of from 0.0001:1 to 0.8:1, preferably from 0.001:1 to 0.5:1.
In a further preferred embodiment, the reaction is carried out in a protective gas atmosphere. Preferred protective gases are, for example, nitrogen and the noble gases, such as helium or argon.
The present invention accordingly relates also to a process for the preparation of compounds of formulae (XXXV) or (XXXVI) and (XXXVII) wherein R11 and R3 are alkyl, preferably methyl, wherein the compound of formula (XXXVa) or (XXXVIa) and (XXXVIIa) is reacted with HCHO or with a formaldehyde-providing compound in the presence of formic acid (Leuckart-Wallach reaction) and a solvent, or alkylated with an alkyl iodide and a phase-transfer catalyst, preferably methyl iodide in aqueous potassium hydroxide solution and triethylammonium chloride.
The reaction is preferably carried out at reaction temperatures in the range of from xe2x88x9210 to 200xc2x0 C. According to observations hitherto, the success of the reaction is not dependent on the pressure range selected. For simplicity""s sake, the reaction is customarily carried out at atmospheric pressure, but it is also possible to select pressures in the range of from 10 kPa to 10 MPa. The reaction times are selected, depending on the reaction temperature chosen, preferably in the range of from 1 hour to 48 hours.
As formaldehyde-providing compound there may be used, for example, paraformaldehyde or trioxane. Formaldehyde can be used in the form of a gas or in the form of a formalin solution.
The molar ratio of formic acid to the compound of formula (XXXVa) or (XXXVIa) and (XXXVIIa) is customarily in the range of from 1:100 to 100:1.
The concentration of the formalin solution is generally from 35 to 37 per cent by weight.
The molar ratio of the formalin solution to the compounds of formulae (XXXVa) or (XXXVIa) and (XXXVI1a) is customarily in the range of from 1:1 to 100:1.
It has proved advantageous to carry out the reaction in the presence of an organic solvent. As solvent there come into consideration, for example, those solvents listed above for the process for the preparation of perylenebisimides (I) wherein A1 is A4. Particularly advantageous as solvent are N,Nxe2x80x2-dimethylformamide, N,Nxe2x80x2-dimethylacetamide, nitrobenzene and N-methylpyrrolidone.
The weight ratio of the compounds of formulae (XXXVa) or (XXXVIa) and (XXXVIIa) to the solvent is customarily selected in the range of from 0.001 to 100% by weight, preferably from 0.001 to 20% by weight.
A special development of the present reaction relates to the use of dipolar aprotic solvents.
As phase-transfer catalyst there may be used, for example, triethylbenzylammonium chloride or triethylbenzylammonium bromide.
The molar ratio of phase-transfer catalyst to compounds of formulae (XXXVa) or (XXXVIa) and (XXXVIIa) is customarily in the range of from 0.0001:1 to 0.8:1, preferably from 0.001:1 to 0.5:1.
In a further preferred embodiment, the reaction is carried out in a protective gas atmosphere. Preferred protective gases are, for example, nitrogen and the noble gases, such as helium or argon.
The reaction product is preferably isolated by precipitation with water and subsequent filtration.
It has proved advantageous to adjust the precipitated reaction product in water to a pH value in the range of from 7.5 to 10 with a base.
As base there may be used, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate or potassium hydrogen carbonate.
The compounds of formulae (XXXVa) or (XXXVIa) and (XXXVIIa) isolated according to the processes of the invention can be purified in accordance with customary methods, such as by chromatography, especially column chromatography, or crystallisation, especially extractive recrystallisation.
In the present invention it has also been found that trialkylphosphonate derivatives (XXXII) and pyrrolo derivatives (XII) can be obtained from the above nitro derivatives of the compounds of formula (XXXIII) by reaction with trialkyl phosphite.
The present invention accordingly relates also to a process for the preparation of perylenebisimide trialkylphosphonates of formula (XXXII) and perylenebisimide pyrroles of formula (XII), wherein the compound of formula (XXXIII) is reacted with trialkyl phosphite of the formula P(OR 12(OR11)(OR5) wherein R12, R11 and R5 are as defined above and are especially C1-C4 alkyl.
Synthesis 1969, 11 to 17, describes methods for the reaction of amines with trialkyl phosphite, so that further details on the subject are superfluous.
The reaction is preferably carried out at reaction temperatures in the range of from xe2x88x9210 to 150xc2x0 C., especially from 100 to 150xc2x0 C. According to observations hitherto, the success of the reaction is not dependent on the pressure range selected. For simplicity""s sake, the reaction is customarily carried out at atmospheric pressure, but it is also possible to select pressures in the range of from 10 kPa to 10 MPa. The reaction times are selected, depending on the reaction temperature chosen, preferably in the range of from 1 hour to 48 hours.
The molar ratio of the nitro derivative (XXXIII) to the trialkyl phosphite is customarily in the range of from 1:1 to 1:500, preferably from 1:10 to 1:200.
It has proved advantageous to carry out the reaction in the presence of an organic solvent. As solvent there come into consideration, for example, those solvents listed above for the process for the preparation of perylenebisimides (I) wherein A1 is A4.
The weight ratio of nitro derivative (XXXIII) to solvent is customarily selected in the range of from 1 to 100% by weight.
In a further preferred embodiment, the reaction is carried out in a protective gas atmosphere. Preferred protective gases are, for example, nitrogen and the noble gases, such as helium or argon.
The pyrrolo and trialkylphosphonate derivatives of formulae (XXXII) and (XII) prepared according to the process of the invention can be purified and isolated in accordance with customary methods, such as by chromatography, especially column chromatography, or crystallisation, especially extractive recrystallisation.
It has proved especially advantageous to separate and purify the pyrrolo and trialkylphosphonate derivatives of formulae (XXXII) and (XII) by column chromatography using trichloromethane as eluant on aluminium oxide.
It has also been found that the pyrrolo derivatives of formula (XII) can be alkylated, benzylated or acylated.
The invention accordingly relates also to a process for the preparation of compounds of formula (XIII), wherein a compound of formula (XII) is reacted with a halide of formula R4-Hal, in the presence of a base.
The reaction is preferably carried out at reaction temperatures in the range of from -10 to 100xc2x0 C., especially from 0 to 50xc2x0 C., very especially from 0 to 30xc2x0 C. According to observations hitherto, the success of the reaction is not dependent on the pressure range selected. For simplicity""s sake, the reaction is customarily carried out at atmospheric pressure, but it is also possible to select pressures in the range of from 10 kPa to 10 MPa. The reaction times are selected, depending on the reaction temperature chosen, preferably in the range of from 1 hour to 48 hours.
As bases there may be used the bases listed above for the process for the preparation of compounds of formula (XXVII).
The molar ratio of base to pyrrolo derivatives of formula (XII) is customarily in the range of from 1:10 to 10:1, preferably from 1:5 to 5:1.
In a preferred embodiment of the process according to the invention, the reaction of a pyrrolo derivative of formula (XII) with a halide is carried out in the presence of a solvent.
A particular embodiment of the process according to the invention relates to the reaction in the presence of potassium hydroxide powder in the presence of a protic solvent. For example, alcohols, such as methanol, ethanol, propanol, isopropanol, n-, sec- or tert- butanol, n-, sec- or tert-pentanol, have proved to be especially advantageous as protic solvents.
In a further particular embodiment of the process according to the invention, there are used generally non-nucleophilic bases, such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene ((DBN) or N,N,Nxe2x80x2,Nxe2x80x2-tetramethylethylenediamine (TMEDA).
It has proved advantageous to carry out the reaction in the presence of an organic solvent. As solvent there come into consideration, for example, the solvents listed above for the process for the preparation of perylenebisimides (I) wherein A1 is A4. Special preference is given to N,Nxe2x80x2-dimethylformamide, N,Nxe2x80x2-dimethylacetamide or N-methylpyrrolidone and to trichloroethane, dichloroethane, trichloromethane or dichloromethane; ethers are especially preferred, with special preference being given to tetrahydrofuran.
The weight ratio of pyrrolo derivative (XII) to solvent is customarily in the range of from 0.001 to 100% by weight, preferably from 0.001 to 20% by weight.
The pyrrolo compound derivatives isolated according to the processes of the invention can be purified in accordance with customary methods, such as by chromatography, especially column chromatography, or crystallisation, especially extractive recrystallisation.
It has also been found in the present invention that the perylenebisimides of formula (XXXIII) are suitable for the nucleus-extension of perylenebisimides with sulfur.
The present invention accordingly relates also to a process for the preparation of compounds of formulae (XIV) and (XV), wherein 1-nitro-perylenebisimides of formula (XXXIII) are reacted with sulfur in the presence of a solvent.
The reaction is preferably carried out at reaction temperatures in the range of from xe2x88x9210 to 200xc2x0 C., especially from 0 to 150xc2x0 C. According to observations hitherto, the success of the reaction is not dependent on the pressure range selected. For simplicity""s sake, the reaction is customarily carried out at atmospheric pressure, but it is also possible to select pressures in the range of from 10 kPa to 10 MPa. The reaction times are selected, depending on the reaction temperature chosen, preferably in the range of from 1 hour to 40 hours, especially in the range of from 5 hours to 24 hours.
It has proved advantageous to carry out the reaction in the presence of an organic solvent. As solvent there come into consideration, for example, the solvents listed above for the process for the preparation of perylenebisimides (I) wherein A1 is A4. Special preference is given to dipolar aprotic solvents, such as N,Nxe2x80x2-dimethylformamide, N,Nxe2x80x2-dimethylacetamide, nitrobenzene and N-methylpyrrolidone.
The weight ratio of solvent to the 1-nitroperylenebisimide of formula (XXXIII) is customarily in the range of from 1:1 to 1000:1, preferably from 1:10 to 500:1.
The molar ratio of sulfur to the 1-nitroperylenebisimide (XXXIII) is customarily in the range of from 10:0.1 to 0.9:1, preferably in the range of from 5:0.1 to 4:1.
In a further preferred embodiment, the reaction is carried out in a protective gas atmosphere. Preferred protective gases are, for example, nitrogen and the noble gases, such as helium or argon.
It has proved advantageous to treat the reaction mixture with dilute mineral acid, such as hydrochloric acid, at a temperature in the range of from 80 to 120xc2x0 C., especially from 90 to 110xc2x0 C., the desired product being precipitated.
If desired, the resulting precipitate can be washed with water and, if desired, the precipitate can be dried.
Furthermore, the precipitate, which may or may not have been dried, can be purified in accordance with customary methods, such as by chromatography, especially column chromatography, or crystallisation, especially extractive recrystallisation.
A further embodiment of the present invention relates to the use of the perylenes (I), (II), (XXX) and (XXXI) according to the invention as colourants, especially as pigments and dyes, in each case in accordance with methods generally known per se, preferably
(a) for melt colouration of polymers, it being possible to use as polymers polyvinyl chloride, cellulose acetate, polycarbonate, polyamide, polyurethane, polyimide, polybenzimidazole, melamine resin, silicone, polyester, polyether, polystyrene, polymethyl methacrylate, polyethylene, polypropylene, polyvinyl acetate, polyacrylonitrile, polybutadiene, polychlorobutadiene or polyisoprene, and the copolymers of the mentioned monomers;
(b) as vat dyes or mordant dyes, for example for dyeing natural materials and, especially, paper, wood, straw, leather, animal skins or natural fibre materials, such as cotton, wool, silk, jute, sisal, hemp, flax or animal hair (e.g. horsehair) and their conversion products, such as viscose fibres, nitrocellulose silk or copper rayon, preferred salts for mordanting being aluminium, chromium and iron salts;
(c) in the manufacture of paints, lacquers, especially automotive lacquers, coating compositions, paper dyes, printing inks, inks, especially for use in ink-jet printers, preferably in homogeneous solution as fluorescent inks, and for drawing and writing purposes, and in electrophotography, for example for dry-copying systems (Xerox process) and laser printers;
(d) for security-marking purposes, such as for cheques, cheque cards, bank notes, coupons, documents, identity papers and the like, where a particular, unmistakable colour impression is to be achieved;
(e) as an additive to colourants, such as pigments and dyes, in which a particular shade of colour is to be achieved; especially luminescent shades are preferred;
(f) for labelling objects for the purpose of mechanically recognising those objects by means of fluorescence, preference being given to the mechanical recognition of objects for sorting, for example for the recycling of plastics, with alpha-numerical printing or bar codes preferably being used;
(g) for frequency conversion of light, for example in order to make longer-wavelength, visible light from short-wavelength light, or for frequency doubling or frequency tripling of laser light in non-linear optics;
(h) for the production of passive display elements for a wide variety of display, information and labelling purposes, for example passive display elements, road signs and traffic signals, such as traffic lights;
(i) as starting material for supraconducting organic materials (via xcfx80-xcfx80 interactions, after doping with, for example, iodine there is usually obtained an intermediate charge delocalisation);
(j) for fluorescent labelling of solids;
(k) for decorative and artistic purposes;
(I) for tracer purposes, for example in biochemistry, medicine, technology and natural science, it being possible to link the colourants according to the invention covalently to substrates or via secondary valences, such as hydrogen bonds or hydrophobic interactions (adsorption); examples thereof are protein-dye combinations, antibody-dye combinations or DNA- or RNA-dye combinations,
(m) as fluorescent dyes in highly sensitive detection methods (see C. Aubert, J. Fxc3xcnfschilling, 1. Zschokke-Grxc3xa4nacher and H. Langhals, Z. Analyt. Chem. 1985, 320, 361), especially as fluorescent dyes in scintillators;
(n) as dyes or fluorescent dyes in optical light-collecting systems, in fluorescent quantum counters, in fluorescent solar collectors (see H. Langhals, Nachr. Chem. Tech. Lab. 1980, 28, 716), in fluorescence-activated displays (see W. Greubel and G. Baur, Elektronik 1977, 26, 6), in cold-light sources for light-induced polymerisation in the preparation of plastics, for materials"" testing, for example in the manufacture of semiconductor circuitry, for the investigation of microstructures of integrated semiconductor components, in photoconductors, in photographic processes, in display, illumination or image-converting systems in which excitation is effected by means of electrons, ions or UV radiation, for example in fluorescent displays, Braun tubes or in fluorescent tubes, as part of an integrated semiconductor circuit, which contain dyes as such or in conjunction with other semiconductors, for example in the form of an epitaxy, in chemiluminescent systems, for example in chemiluminescent light rods, in luminescent immunoassays or other luminescent detection methods, as highlighter inks, especially for lending visual prominence to text and drawings or other graphic products, for identifying signs and other objects where a particular visual colour impression is to be achieved, in dye lasers, preferably as fluorescent dyes for producing laser beams and as Q-switches;
(o) as rheology improvers and
(p) for modifying inorganic solids, such as aluminium oxide, silicon oxide, for example, in zeolite cages, titanium dioxide, tin oxide, magnesium oxide (xe2x80x9cxylolithxe2x80x9d), silicates, clay minerals, chalk-, gypsum- or cement-containing surfaces such as paints or plaster surfaces in which the free carboxyl function provides special adhesion to the surface, or
(q) as NIR dyes for information technologies.
In particular, the compounds wherein R1 and/or R2 is/are 1-butyl-pentyl, 1-hexyl-1-heptyl, 1-heptyl-1-octyl, 1-octyl-1-nonyl, 1-nonyl-1-decyl and 2,5-di-tert-butylphenyl are distinguished by their good solubility.

Abstract: intermediates in the preparation of compounds (I) and processes for the preparation of those intermediates and also processes for the preparation of compounds, (I), and the use thereof as colorants.


A control area is imaged on photo-sensitive graphic arts material to be evaluated for the sharpness of images printed on the material through the various stages of the reproduction process. The control area includes a light transmitting image divided into a plurality of segments where the image is a sharp-edged line element of a fixed preselected width. The line element is repeated from segment to segment in a preselected pattern of line elements separated a preselected distance apart by a space. The first segment of a control area has a solid optical density. At the opposite end of the control area is positioned a second segment having a substrate optical density. An intermediate segment includes a plurality of sections in which the line elements in each section are spaced apart the same distance, and the spacing between line elements varies from one section to the next. Thus, a range of spatial frequencies of repeating line elements is provided in the control area. By using an integrating densitometer, the optical density at any section at a desired frequency below the solid optical density is measured. At the desired frequency, a theoretical optical density is calculated. The ratio of the theoretical integrated optical density to the measured integrated optical density provides an index of acutance which is 1.0 for a perfectly image line element. If the index is unacceptable, the width of the line element is altered by a calculated correction factor to achieve an acceptable index of acutance.

1. Field of the Invention
This invention relates to a device for quantitatively measuring the visual sensation of the sharpness of an image printed on a substrate and more particularly to a method and apparatus for determining an index of the acutance as a quantitative indication of the quality or sharpness of a image for graphic arts films, offpress proofs, press proofs, printing plates, printed press sheets and the like.
2. Description of the Prior Art
In the photographic industry the term "sharpness" has been used to describe the subjective impression produced by the edge of a image in the brain of an observer and the optical density distribution as measured by some objective criterion. However, because sharpness is a psychometric evaluation based on a number of factors an objective measurement of image sharpness has not heretofore been obtainable. The various factors that enter into a determination of sharpness include image register, subject matter, edge enhancement, density range, and resolution.
More recently, the term "acutance" has been used in the photographic industry to distinguish between the subjective impression of sharpness and the objective measurement of the optical density gradient made by a microdensitometric trace across the edge of an image. It has been generally recognized that image sharpness is a subjective concept that can not be objectively measured. Nevertheless, those skilled in the art have felt that a correlation might be formed between the subjective evaluation of image sharpness and acutance measurements made with a microdensitometer.
One known approach is to utilize a series of photographic prints of the same subject but differing degrees of sharpness. The sharpness is manipulated by using different negative materials. Observers then rank the photographic prints according to their sharpness. General agreement is found between the rankings, and the data is manipulated to provide numerical values for the subjectively determined sharpness. However, these efforts overall indicate that there is no satisfactory correlation between image sharpness (acutance) and resolution where resolution is defined as an ovserver's ability to distinguish closely spaced line pairs under adequate magnification. The efforts to find a correlation between the psychometric evaluation of sharpness and an index of acutance calculated from edge density tracings have led to the conclusion that set by the eye for a given viewing condition. However, this approach has indicated that resolving power is not found to furnish consistent information about the perceived sharpness of prints.
Efforts have also been made to examine the effect of sharpness and resolving power on image definition which is regarded in the art as the quality aspect of the photo that is associated with the clarity of detail. Sharpness then by some authorities has been recognized as the impression made on the mind of an observer when examining the boundaries of well resolved elements of detail. In application of these theories, experiments have been conducted utilizing a series of photographic prints on which the graininess and tonal characteristics were held constant by using the same materials in processing for all prints. Sharpness and resolution were varied by changing the distance from the lens to the film. A three-part test subject consisted of a photographic image to be judged for definition, a graduated set of lines for determining resolving power, and a sharp-edge element for measuring acutance. These experiments led to the conclusion that when graininess and tone reproduction are constant and resolving power is adequate to reproduce all the detail that can be observed under the conditions of viewing, acutance correlates well with definition. However, resolution becomes an important component of definition if it drops below the value required to render all the detail that can be observed.
Additional experiments have been attempted in the past to develop means of evaluating and quantifying print quality attributes that ca be distinguished as independent of the subject matter of the image. One approach has been to utilize a star target formed of a circular series of pie-shaped wedges. Star targets are well known for use in measuring the resolution of camera lenses and have proved adequate for measuring the resolution of lithographic printing.
Based on the premise that the observer's impression of sharpness can be predicted from microdensitometric traces across sharp edges in the image, it has been proposed by some authorities that a more complete description of an image could be to determine the ratio of the reflectance changes across various size detail or lines in the original image to their corresponding reflectance change in the lithographic print. With this approach, a scanning microdensitometer is used to determine an edge gradient profile from which a spread function is calculated. Fourier transforms of the spread function are used. The presence of slur, image spread, and doubling had the effect of adding higher harmonics into the sine wave analysis.
The acutance of typed images has also been measured using video camera input. With this approach, acutance is defined as the summation of density differences of pixels in the type in relation to the upper and lower thresholds for density. Edge smoothness is calculated in terms of the standard deviation of pixels from the regression line representing a theoretical sharp edge. Several reproduction systems are compared with respect to their acutance and edge smoothness.
In lithography, various aspects of image structure are related to print quality, where the overall image definition is influenced primarily by resolution and sharpness. Three distinct components of image sharpness have been recognized as including the minor contrast of the printed image, the register accuracy in process color work, and the edge enhancement performed on the image during the color separation process. It is generally recognized that substrates with high brightness and low internal light scatter have greater sharpness. Furthermore, images with higher density range have higher sharpness. Also, it has been found that by increasing ink film thickness, the density range is increased but resolution is lowered.
The register latitude for a given picture varies with the amount of detail and color contrast in the image and with the screen ruling selected for the job. Edge enhancement is a variable and depends on the preferences of the customer, the sharpness of the photographic original and the requirements of the printing system. Optimization conditions are not clear in the case of sharpness. In practice, compromises are necessary between optimum sharpness and the needs for tone and color reproduction.
It is also known to use electronic scanners for making color separations to provide the means for reproducing a considerable range and magnitude of electronic edge enhancement effects through unsharp masking. Three functions are accomplished by unsharp masking. It must correct for the modulation transfer function limitations in originals due to the materials and imaging equipment. It must allow for limitations of the reproduction process. It must also provide a means for editorial change to alter the visual impact of the image. The performance of unsharp masking in electronic scanners is constrained by considerations of resolution, screen, intensity, fringing, and enlargement. Sharpness appearance is influenced by tonal reproduction and frequency response. One approach has been directed to the need for the inclusion of edge effects in the brightness model.
In an effort to measure and evaluate image sharpness, the printing industry has found for some imaging systems that the calculation of acutance from microdensitometric traces has a correlation with perceived sharpness. However, this technique is not available to the printer since it involves specialized equipment. Accordingly, as an alternate means for calculating acutance, the printing industry has developed targets or guides that include line elements which vary in size and frequency. However, the known targets and guides are used solely for the measurement of resolution and not for a quantitative determination of image sharpness.
U.S. Pat. No. 3,393,618 discloses a guide or a control strip for use in the preparation of printing plates in order to determine if the printing operation is running properly. In this context, it is important to determine whether the plate is under developed or over developed, under exposed or over exposed. Then it must be determined once the plate is on the press whether or not the print quality is proper. In an effort to obviate these problems, a control strip in the form of a stencil is placed on a plate by a photographic process, either positive or negative. The control strip is an image bearing item, normally a negative, and is handled by the plate maker so that the image therefrom is located on the plate in a manner designed to measure and inform the plate maker and the pressmen of proper conditions. Preferably, the control strip is located on the edges of the plate so that it can be removed from the resulting print without effecting the print. The control strip has a pattern which is used to determine the condition of the plate and will indicate a gain or loss in image and will indicate any over or under exposure. Reference patterns are located adjacent to each other and the patterns may consist of any geometric design, such as round dots or parallel lines. If the image on the plate is proper then the different reference areas will appear to have equal visual tone. If any over or under exposure or development has taken place in preparing the plate, then the small signal design area of the control strip will change in visual tone proportionately more than the large reference area. This produces a recognizable pattern which informs the plate maker that his plate is improper.
U.S. Pat. No. 3,998,639 discloses a test pattern for determining deviations in the formation of masks used for printing electronic circuit patterns on a photoresist film on a wafer surface. The test pattern includes a grid of lines spaced a preselected distance apart so as to appear as a gray area. The shade of the gray area changes significantly as the width of the lines is altered. To determine if the width of the lines of the test pattern has deviated from a preselected width, a plurality of reference patterns having a preselected deviation from the desired width of line are printed along with the test pattern on the reference plate. If the test pattern has a shade of gray that falls between the two reference patterns, then it is concluded that the test pattern is deemed to be satisfactory because the deviation in the shade of the gray pattern is readily observable.
U.S Pat. No. 4,004,923 discloses a test film target used as a control guide for monitoring developer activity in automatic plate processors to show dot size change in printing and dot size change in bi- and tri- metallic etching. The guide includes a film laid-down on a border or other non-printing area of the negative or positive film and exposed together with the original film to be reproduced on the photosensitized printing plate. Visual observation of the reproduced guide on the plate with the negative eye permits readout of developer solution activity and provide a means for determining when replenisher must be added to the developer solution or a diluent for the developer fluid must be added before any diminution or increase in the strength of the developer has any noticeable effect on the reproduction of the original film. The test film target includes a number of tint areas such as a 1/4 inch circle of 200 line per inch tints. The tints are composed of crossed bands and the width of each band increases in a progressive manner. Since each of the fine tint circles has different band widths, one of the circles will match the background in integrated optical density or tonal effect and therefore, blend together with it. Accordingly, when exposure and development are optimum, the test film will usually blend at a prescribed tint circle. However, when the background does not blend at the prescribed tint circle, an adjustment must be made in the developing process such as adding replenisher to the developing film, if sufficient replenisher is added, the prescribed tint circle will once again blend into the background. With this arrangement, a visual indication of exposure conditions is obtained.
U.S. Pat. No. 4,183,659 is directed to the problem of controlling variations of the thickness of the lines forming the text appearing in a photographically produced brief. The control device in the form of a screen or raster area is printed by photographic means on the photographic print carrier. The screen area may include dots or lines having preselected widths and preselected distance or gaps therebetween. If during the exposure and development of the print carrier, an increase in the thickness of the lines occurs, the spaces or gaps will be filled out and the screen area will turn completely black. On the other hand, in the event a decrease of the thickness of lines occurs, the lines or screen dots in the screen or raster area decrease to an extent that they disappear. Therefore, undesirable broadening or narrowing of the lines in the screen area requires visual detection by the human eye or by means of a densitometer.
U.S. Pat. No. 4,288,157 is a further example of apparatus for controlling the quality of a picture, such as a screened print, processed in a reproduction process. The quality of the screen print is determined by such factors as resolution power, tone displacements, screen dot formation, color layer thickness, and grey balance. In order to evaluate the quality of the screened print based on the above factors, a control device consisting of a number of measurement symbols, such as screen dots, are printed in a preselected array on the picture carrier upon which the printing process is performed. Deformations in the measurement symbols are monitored as the carrier advances through the various stages of the reproduction process. When a deformation occurs in the shape or size of the measurement symbol, the deformation occurs uniformly in all directions during the production process. Therefore, the deformation will become visibly noticeable when a recess or space between the symbols disappears. Upon the disappearance of a recess with a known width, it is concluded that the measurement symbol has reached a certain dimension that has exceeded an acceptable degree of deformation. Then from the value of the known relationship between the original surface of the parts of a measurement symbol of the control device and the size of the recess at such measurement symbol, it is then possible to draw conclusions about the size of the enlargement of the screen dots of the reproduced picture.
U.S. Pat. No. 4,419,426 discloses method and apparatus for visually inspecting the reproduction quality of drawing elements exposed by means of a cathode ray tube on light-sensitive photo material. Visual inspection of print quality to determine whether or not the print is over or under exposed is accomplished by exposing a control field by a cathode ray tube on light-sensitive material. The field includes three different raster points which are combined into a control field. The control field is co-exposed at the beginning and at the end of a text column. If conditions arise during the exposure or development process which result in a change of density and stroke thickness, then an over exposed or under exposed condition can be perceived. If no change in density and stroke thickness occurs, then the control field appears as a neutral gray surface readily identified by the negative eye.
U.S. Pat. No. 4,527,333 discloses a method and apparatus for indicating a quantitative change in dot area of a image in a printing process. The device has particular application in a halftone printing process to quantitatively determine the changes in halftone dot area as an indicator of an increase or decrease in dot area for graphic arts films, prepress proofs, printing plates, printed press sheets, suitable photomechanical processes and the like. The device includes a square matrix array on a substrate. The array comprises a combination of dots and squares where the dots and squares are each equal in size. A dot is positioned in the center of an array with the squares equally spaced around the center dot and the remaining dots positioned at each corner of the square array. The members of the array are spaced a preselected distance apart forming gaps between the adjacent dots and squares. Upon the occurrence of a dot gain, the adjacent sides of the squares touch the dots. As the dot gain increases, the sides of the squares and circumference of the dots merge and overlap so that the gap disappears. With this arrangement, the size of the gap between dots and squares is selected so that the growth of the dots and squares to close the gap will indicate a given dot area gain or dot area loss.
U.S. Pat. No. 4,566,192 is a further example of a device that includes a pattern for determining the dimensions of projected or printed figures. A geometric pattern is used to maintain accurate dimensions during the manufacture of semiconductor wafers.
While it is has been suggested by the prior art devices to evaluate the resolution quality of an image to be reproduced in a printing process, the known devices rely upon visual evaluation of a control device, pattern, measurement element or the like to identify deformations in the reproduced image. The devices depend upon amplitude modulation for an indication of the print quality. This requires that the printed matter be visually inspected to determine whether the quality is acceptable. In the alternative, the reproduced image can be quantitatively analyzed by use of a microdensitometer. However, the use of a microdensitometer requires substantial technical expertise which is generally beyond the capability of the individual who must evaluate the print quality at the production stage.
Therefore, there is need for a device capable of providing a quantitative measurement of the acutance or sharpness of a reproduced image at various stages in the reproduction process. The device must be capable of being used efficiently by the personnel involved at the various stages in the reproduction process.

Frequency modulated acutance guide and method of use


A rotor cover designed with a sealing surface interacting with a compressed-air connection, whereby the compressed-air connection is effected via a connecting piece located between the rotor cover and the appertaining mounting plate.

The invention relates to a cover of the spinbox of a rotor spinning machine. It also relates to a mounting plate for the attachment of the cover.
A cover of this type is known from the rotor spinning machine RU 14 of Schubert & Salzer, Maschinenfabrik Aktiengesellschaft, Ingolstadt, Federal Republic of Germany. Such covers, which are called rotor covers for short in the jargon used by specialists in the field, constitute part of the wall of the spinbox in which the spinning rotor rotates. Since the spinbox must be subjected to negative pressure during the formation of yarn it is closed and is usually subjected to active suction. The spinbox must be opened for maintenance of the rotor, e.g. for mechanical cleaning of the rotor and sometimes also for pneumatic rotor cleaning. This also applies when the rotor is to be replaced. The spinbox is opened by opening the cover which constitutes the rotor box or spinbox wall across from the open side of the spinning rotor.
For this purpose the cover is attached to a mounting plate which, in turn, constitutes the cover of the rotor box and is attached to the machine frame, for example, so as to be capable of pivoting in relation to the rotor. Such a rotor box is shown in German Patent Publication No. DE-OS 28 11 960, for example. Among other things, FIG. 2 of this publication shows a cover bearing the reference number 36. For the sake of simplification the mounting plate was omitted in this drawing. In the state of the art it is installed on the side of the cover away from the spinning rotor and, in turn, attached to the cover which is cover 32 in the drawings of No. DE-OS 28 11 960. As can be seen in the drawings of No. DE-OS 28 11 960, the cover not only serves to cover the rotor box but in addition contains a channel to feed fibers into the rotor. Bores for the arrival of cleaning air into the rotor as well as a bore to draw the yarn produced in the rotor out of the rotor box are also contained in the cover.
In a manner not shown in the schematic representation in the publication, the cover has a threaded bore in its back away from the rotor for connection of compressed air for rotor cleaning and a bore into which a yarn draw-off pipe is inserted from the back. It is connected to the cover by a stud screw running at a right angle to the bore.
The known rotor cover consists of an aluminum pressure-cast element that must be machined after casting. Especially threads for compressed-air connection and for the attachment of the yarn draw-off pipe must be installed and this causes an additional machining outlay. The known rotor cover forms a component on the rotor spinning machine which must be replaced from time to time by the operator of the machine. When the machine is changed over to a different yarn which is produced with a rotor of different diameter, the rotor cover must be replaced. The disadvantage of the known cover is that it is difficult to install and to remove. Due to the fact that the compressed-air circuit is connected by means of threads, the compressed-air circuit must first be removed in order to replace the cover and must be re-connected to the new cover to be installed, requiring the use of tools. The yarn draw-off pipe is also removed from the machine together with the removal of the rotor cover since it is firmly connected to the cover. As a result it must be removed from the disassembled cover and replacement of the yarn draw-off pipe, which is a wear part of the rotor spinning machine, is not possible without disassembly the cover.
The known mounting plate to which the cover is attached is provided with a contact surface upon which the rotor cover bears, as well as a threaded bore to screw on the rotor cover. Near the cover's air connection and yarn draw-off pipe the mounting plate is provided with a recess so that when the fastening screw of the cover is loosened, it may be removed together with the air connection and the yarn draw-off pipe. Air connections and yarn draw-off pipes remain firmly connected to the cover and must be removed from it later. This is awkward because of the lack of space and is time consuming. The installation of a new cover is accordingly complicated.

Cover of a spinbox of a rotor spinning machine

Rieter Ingolstadt Spinnereimaschinenbau AG


Large-area, low-cost single crystal transparent gallium-containing nitride crystals useful as substrates for fabricating GaN devices for electronic and/or optoelectronic applications are disclosed. The gallium-containing nitride crystals are formed by controlling impurity concentrations during ammonothermal growth and processing to control the relative concentrations of point defect species.

The present invention generally relates to processing of materials for growth of crystals. More particularly, the present invention provides a transparent gallium-containing nitride crystal synthesized by an ammonobasic or ammonoacidic technique. The present invention provides methods suitable for synthesis of polycrystalline nitride materials, as well as other crystals and materials. Such crystals and materials include, but are not limited to, GaN, AlN, InN, InGaN, AlGaN, and AlInGaN, and for manufacture of bulk or patterned substrates. Such bulk or patterned substrates can be used for a variety of applications including optoelectronic devices, lasers, light emitting diodes, solar cells, photoelectrochemical water splitting and hydrogen generation, photodetectors, integrated circuits, and transistors.
Gallium nitride containing crystalline materials serve as substrates for manufacture of conventional optoelectronic devices, such as blue light emitting diodes and lasers. Such optoelectronic devices have been commonly manufactured on sapphire or silicon carbide substrates that differ in composition from the deposited nitride layers. In the conventional Metal-Organic Chemical Vapor Deposition (MOCVD) method, deposition of GaN is performed from ammonia and organometallic compounds in the gas phase. Although successful, conventional growth rates achieved make it difficult to provide a bulk layer of GaN material. Additionally, dislocation densities are also high and lead to poorer optoelectronic device performance.
Reasonably high quality, substantially transparent substrates comprising bulk gallium nitride are available commercially, however, in most cases, these substrates are synthesized by hydride vapor phase epitaxy (HVPE), which is relatively expensive.
What is needed is a method for low-cost manufacturing of transparent nitride materials that are transparent, colorless, and of high crystallographic quality.

Transparent group III metal nitride and method of manufacture