DE1645905A1 - Process for the preparation of 3,3-disubstituted indoline derivatives - Google Patents

Description

1645Q05

intended for
Disclosure

P..16 45 905.5-44 February 5, 1970

Allied Chemical Corporation, New York, N.Y., USA

Process for the preparation of 3,5-disubstituted Indoline derivatives

The object of the invention is to produce new 2- (Aryliminop © lymethiß) -3,3 ~ ais ^ fcifcwi® ^ ®3? Indolines which do not contain any groups with ionizable hydrogen and in which the polystyrene radical is not a conjugated chain of elaer straight «10; exceeding number of carbon atoms is, ale sis J @ deia silk | a double bond bsslfcst and over as · B © pp®Ibindusig at its one end to the nitrogen atom dss »Arflaüti & agruppe and via di® DoppeIbisidimg to the tncternm Enä® to öas Cg-At-ORi of the IndGlink @ rti @ s gssbusideß isfc. Des ¥ @ E ^ fater3rj is ·· characterized by «« JaS eis vor * isiiisiirbeess stoff FimL && 3f? * Disubstituted indoline <2erivs'B the 2'active group in the 2-position is deceptive *

009823/1799
Documents yes «. / ιια & », 2 μγ.ι

arylamino derivative free of ionizable hydrogen is converted to the polymethine compound mentioned. The process product * are new electron donor compounds that are faintly colored or are practically colorless, but in connection with acidic electron acceptors, intense colors in the yellow to generate the red part of the visible spectrum. They can be used as color precursors in duplicating systems to produce intense red to yellow To achieve colorations.

The manufacture of electron donor compounds that are weakly colored to practically colorless, but result in colored substances when they are with acidic electron acceptors such as kaolin) bentonite and other acidic clays, zinc sulfide, Calcium fluoride and organic acids (e.g. tannic acid, Benzoic acid and succinic acid) are brought together,

is known.

The valuable properties of said known chromogenic compounds have led to the development of compositions, SA * of which are useful in the production of so-called. "Farbloeen carbon papers" and variations. For example, impact printing papers and reproduction / duplication systems of this type are known in which a solution of bis- (p-dimethylaminophenyl) -methyl-anlline (never an ohromogeneous electron donor compound) in the form of individual ones

009829/1799

16452C5

-χ.

Particles in connection with a solid insulating material, which consists of an organic hydrophilic film-forming substance and an acidic clay is present. On pressure a combination of the chromogenic takes place with a pen or with a punch, e.g. with a typewriter type » Combination with the acidic, electron accepting clay, causing a blue color mark. Furthermore, systems are known in which in a number of ^ superimposed sheets cover the back surface of each top sheet with a dispersion of a suitable one Solution of the chromogenic substance coated in a ripenable hydrophilic colloidal film and the surface facing this rear side of the respective underlying Sheet is coated or filled with an acidic, electron accepting clay. By pressing with a pen or by striking the upper sheet, color formation occurs on the surface containing the acid clay caused the pressure or stop points. "

For these electron donor compounds in combination other uses have also been developed with acidic electron accepting substances, but lead Most of these compounds, which are known to date, cause colorations that are mainly on the blue to green Area of the visible spectrum are limited.

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In contrast, the first-mentioned new compounds, particularly those in which the three substituents are alkyl groups, particularly advantageous properties, the Give them a special value for the purposes mentioned and they especially for the production of make yellow to red colorations suitable.

The new compounds are formed by three residues in such a combination that &_& q the compound is given color-forming resonance when it is protonated or brought into contact with an acidic electron acceptor: 1) A polymethine radical consisting of a conjugated chain consists of an even number of carbon atoms not exceeding 10 and with a double bond at both ends (ie a vinyl radical · (ethanediylidene radical) or an unbranched chain of 2-5 vinyl radicals)? 2) a 2,3-disubstituted indoline radical free of ionizable hydrogen with a double bond in the 2-position (ie a 3,3-disubstituted indolinylidene radical free of ionizable hydrogen), which is bonded to one end of the polymethine radical via the double bond mentioned and in the 1-position is unsubstituted, but 1-4 substituents free of ionizable hydrogen (which can be the same or different) in the benzene nucleus of the radical (ie in the 4-,

00982S / 17S9

5-, 6- and or or 7-position) and 3) an arylamino radical free of ionizable hydrogen (ie an inner radical in which one of the ammonia hydrogen atoms is replaced by an aryl radical free of ionizable hydrogen), which is attached to its nitrogen atom the other end of the polymethine residue is bound via its double bond.

The compounds can thus gee & e of the invention the formula

,1

(* CH-CH) _n »NA

are represented «in the R a Kalogen-, Hitro- * Alkyl-, Alkoxy-, Cycloalkyl-, üralkyl-, aryl-, Alky! sulfonyl-. Ary, sulfonyl or sulfamyl group and, if more than one Best E is present. Sie Raste R smooth dsS © s? can be different; E w & ü 1% who could be equal or equal to, mean Ha3.ogea » ₉ AIl ^ I-, Cyeloalkyl-, Aralkyä- or Axylgrup'pen? .ic a ganse 2ahl v © n 0-4, a © las gaiase number from l-§ unA A a Ärylr ^ st, ü®? fs "iv" a

003Ö2S / Ϊ799

^R y

in which R has the meaning given above and y has a integer from 0-5 is »mean.

The compounds according to the present invention include compounds in which the benzene nucleus of the xndolinylidene radical is not substituted at all or is substituted by 1-4 inert identical or different radicals (identified by E in the above formula). H can mean, for example, halogen atoms and the following radicals: alkyl and alkoxy (particularly low molecular weight ”), cycloalkyl, aralkyl, aryl (particularly from the phenyl,” naphthyl and biphenyl series), nitro, alkylsulfonyl , Arylsulfonyl and sulfanyl radicals. Representatives of such substituents are the following beds: chlorine, bromine, fluorine, methyl, ethyl, propyl, butyl, amyi, hyxyl _f chloroethyl hydroxypropyl, xthoxylfchylj üytnoitiiyi, methoxy, ethoxy ₃ propoxy, butoxy, amoxy, hexoxy * cyo lopenty ?, Htphthyl, Methylsulforsyl, XthylsuXfonylj Phtnylsulfonfi, Maphthyleulfonyl _s Sulfialdo: - I Cjrelobtxyl »benzyl, Phenltfryl" phenyl, Tola

and ir-Xtbyl

Far"? jgthSrth au 4tn mmn Bv ^ mtmmm, Verbiwdyßf · »^ ia üurn

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the 2,3-substituents of the Indolinylidenreetee, characterized in the above formula by R ₁ and R ₂ . identical or different and in each case halogen. Alkyl (especially low molecular weight), cycloalkyl, aralkyl or aryl (especially from the phenyl, naphthyl and biphenyl series) can be.

The arylamino groups of the new compounds include groups

of various £ which are free of ionizable hydrogen

primary arylamines (special ones from the phenyl, naphthyl and biphenyl series) including those in which the

Aryl nuclei (denoted by A in the above formula)

no further substituents or 1-5 identical or contain various core substituents that are devoid of are acidic, ionizable hydrogen-containing groups.

The more valuable compounds are those where the

Formula R given above is hydrogen, R ₁ and B _{0 are} alkyl. G groups, especially air-substituted alkyl groups of low molecular weight. In particular, methyl groups are and A is a mononuclear aryl radical and in particular a phenyl radical or an alkoxyphenyl radical with an alkoxy group of low molecular weight (especially a methoxyphenyl rest) is.

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Examples of compounds according to the present invention are: 2-f> henyl imino-vinyl) ~ 2,3-dimethyl-indolini 2-4 »henylminovinyl) O * 3 ~ dietnyl-indolini 2- (phenyliminovinyl) -3,3-dibufcyl-indolime 2- (phenylimino-vinyl) -5 »? - dibenzyl-indolinj 2- (phenylimino-vinyl) -3-methyl-3-llthylindolinj 2- (Phenylmino-vinyl) -ö -chlorO ^ -dimethyl-indolinj

2- (Phenylimino-vinyl 1) -4-ethoxy-2,3-diethy 1-indole; 2- (Phenyl imino-vinyl) -5-sulfamyl-J-methyl - ^ - xylyl-indole in; 2- (phenylimino-vinyl) -J-methyl-J-cyclohexyl-indoline; 2 - (Pheny! Imino -vinyl) -5 -hexy! Sulfonyl -3.3-dibuty 1 - indole in?

2- (o-Toluylimino-vinyl) ~ 3,2 ~ dlmethyl-indolim 2- (p-toluylimino-vinyl) -5,3-dlethyl-indoline; 2- (p-toluylimino-vinyl) - ^ »^ - dibengyl indoline; 2- (o-Methoxyphenylminovinyl) «• ^ -iiiethyl-5-ethyl-indoline; 2- (o-Methoxyphenylminovinyl-6-chloro-3 * 2-dimethyl-indolini 2- (p-Methoxyphenyliminovinyl) -4-ethoxy ~, 5-diafchyl-indoline and the corresponding 2- (arylimino-2-bufcen-diylidene) -5 »3-disubstituted Indolines and the corresponding 2- (aryl-imino ~ 2,4 ~ hexadiene diylidene) -3 * 3-the substituted indolines and the corresponding 2- (arylimino-2,4,6-oefcatriendiylidene) -5 »3-dleubatituated indoline.

In contrast to the dyestuff crystal of the azocyanines, which are a quaternary nitrogen atom contain «that by an odd number Methine chain to an xoannular amine stick off atom is bound contain the compounds of this invention

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16459Ü5

a secondary nitrogen atom that is a part of the indoline nucleus and through an odd-numbered methine chain is bound to an exoannular amine nitrogen atom.

The preferred compounds of this invention are pale colored or essentially colorless. When they are protonated, i.e. when brought into contact with an electron accepting substance, they generally give deep, yellow to red colorations, which are generally stable and lightfast.

The new compounds are in a large number of Solvents soluble. So they are not only in the usual solvents such as benzene, toluene, diootyl phthalate and chlorinated Blphenylene soluble, but also have a considerable solubility in petroleum hydrocarbons such as kerosene « white mineral oil and petrol hydrocarbons, as well as In alcoholic solvents such as methanol, ethanol. Diet hy1englycol and glycerin. These properties make the new connection kiaese extremely suitable for expansion of the spectrum of colorations in the systems and Koai positions of the above type can be achieved.

For example, the “new” connection will come in handy colorless 1st and the following structural formula

009829/1799

- ίο -

^13th J ~ \

CH-CH = K- σ J

\ ssssf

possesses> protonated after contact with an acid, and the resulting connection has the following resonance structure, which gives it its deep coloring:

The compounds of the invention are made by reaction of a 3,3-disubstituted indoline, which is a suitable reactive group as a substituent in the 2-position des Indolinkem * possesses, with a suitable arylaeino compound, which binds to said reactive

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- ii - 164590F

Group can enter into a conjugated chain of an even, 10 non-calculating number of carbon atoms, which has a double bond at each end. This chain connects the aryl radical with the via its nitrogen atom Cg atom of the 3,3-disubstituted indoline residue, this one The process is illustrated by the following reaction equation ι

P. L.

1 2
where ft, R, R, A and χ «11« have the meaning given above and Q and Y groups are »ill« to one another »

"Rest react" could η that the Cg "Atoss that 5,3-disubstituted IMoliarestea with the «H-A-R®sfc connects, and η is an integer from 1-5.

The Zugängliehkeit of starting materials after the exercise (aspect and complexity of the apparatus DarsteXlungsmethode simplest consists in the condensation of a free of ionizable hydrogen 3,3-diaubstitulttrten

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Indoline-2-aldehyde, ie a compound "in which Q" is "CH-CHO or" CH (-CH = CH) _n -CHO, with a primary arylamine that is free of ionizable hydrogen-containing groups "ie a compound in which Y «is H ₂ .

This condensation reaction takes place in the presence of an acidic one Catalyst or condensation agent, e.g. of phosphoric acid, hydrochloric acid, sulfuric acid, succinic acid, acetic acid and any other substance that has a pK value of at least about 10. The condensing agent is preferably in at least equimolar amounts Amounts present, based on the amount of indoline compound used. Less amount of condensing agent slow down the rate of reaction, while more than the 10-fold molar excess has no major influence has the reaction rate as the preferred amount.

The reaction is preferably carried out in a solvent carried out. However, substances "which do not react with the reaction components" can be used as solvents in them one »preferably both reaction components are soluble, can be used. In most cases this is the case Substances with hydroxyl groups such as aliphatic «alcohols (e.g. methanol, ethanol, propanols, butanols, pentanols,

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Hexanols, heptanols and octanols) and glycols (e.g. ethylene glycol, diethylene glycol and trimethylene glycol) are suitable * Ethers, such as diethyl ether, can also be used, either alone or in mixtures with one or more of the solvents containing hydroxyl groups. In In many cases, the acidic catalysts or condensates themselves, such as aqueous hydrochloric acid or Acetic acid, act as both a catalyst and a solvent.

The reaction temperature can vary over a wide range. They are not very important in the process. However, they help within limits to accelerate the condensation and in this way to arrive at an acceptable reaction time. Accordingly, it is generally preferred temperatures of from about 5O to about ⁴ carbon iBCK. For reactions that are carried out below about 50 ⁴ C, inappropriately long reaction times are required, while at temperatures much higher than 180 ¹ C, decomposition and side reactions get the upper hand and can in this way reduce the yield of the desired compound.

I am the preferred manufacturing process for the new Ver The invention is as follows! One heats up

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a Gemiech from virtually Kquimolaren amounts of a 2,3-disubstituted indoline -, & ^{2 'a} -acetaldehyds or a related Alkenais and a prijelren arylamines, dissolved in a solvent such as isopropanol, at reflux. To this end, a solution of about twice the molecular weight of phosphoric acid in the solvent mentioned is slowly added to the boiling solution and the mixture is refluxed for a long time (* .B. 5-24 hours) to complete the condensation. The resulting insoluble product is separated from the liquid phase (eg * duroh decanting), dissolved in water and precipitated again by making the solution alkaline to brilliant yellow. For cleaning, it can be dissolved in a suitable solvent (eg acetone) and precipitated again by adding a dilute aqueous alkali solution.

The following are used for the large number of 3,3-disubstituted indoline-2-aldehydes and primary Arylarainen, which are used for the preparation of the compounds of Invention in the catfish described above are suitable Examples given!

3,3-disubstituted indoline-2-aldehydes: 3,3-dimethyl-indoline-Ä ² ' ^a ~ acetaldehyde 3,3-diethyl-indoline-A ^{2> a} -acetalde-

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hydj 2 3-dibutyl-indoline-A ² ' ^a -acetaldehyde | 3,2-dibenzylindoline-Δ ² * ^a -aetaldehyde; 3-methyl-3-ethyl-indoline-Δ ² * ^a acetaldehyde: 6-chloro ~ 3,3-diinethyl "indoline-A. * -Acetaldehyde! 4-Xthoxy-3,3-diSthyl-indole In- Λ ² * ^a -acet aldehyde j 5-sulfamyl-2-methyl-3-xylyl-indoline-A ' ^a -acetaldehydi 5-methyl 3-cyclohexyl-indoline-A ^ -acetaldehydej 5-hexylaulfonyl-3 * 3- <iibutyl-indoline- A ² * ^a -acetaldehyde and the corresponding 2,5-disub-substituted indoline-2-crotonaldehydes, the corresponding ^ »^ - dieubstituted indoline-2,4-sorbsldehydes and the corresponding 3» 3-disub-3-substituted indoline-2,4, 6-octatrienale.

Primary arylamines; Aniline; ο-, «? ~ and p-toluidine; Xylidine; o-, m- and p-anisidines o>, m- and p ~ thoxy-aniline $ t-butoxy-aniline; Ν, Ν-diethyl-phenylenedianiine; J-Uhlor- and 2-bromo-aniline 4-bromo-and 4-chloro-aniline 2-triHluoromethyl-aniline ν amino-biphenyl; m-hitraniline; N'.N'-Dipropyl-sulfanilamidf i- and 2-naphthylamine; 1-amino-4-methoxy-naphthalene »4,4 * -diamino-diphenylsulfone; Benzidine; 2.2 ^I- biphenyl diamine; o- and p-toluidine and o- and p-dianieidine.

Certain embodiments of the invention are described in the following examples. Parts and percent indicated are based on weight, unless otherwise stated. The specified volume percentages correspond to the volumes of the

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numerically the same amount of water by weight

example 1

To the solution one heated to reflux at about 80 ° C Solution of a mixture of 9.4 parts of 3,3-dimethylindoline ~ 2-acetaldehyde (3,; 5-dimethylindoline "A" -acetaldehyde) and 6.2 parts of p-anisidine in about 80 parts of xsopropanol a ventilation of 7 parts by volume within about 15 minutes Drop orthophosphoric acid in 15 parts by volume of isopropanol " added wisely. The mixture is refluxed for about 4 hours and then at for about 40 hours Left to stand at room temperature. The resulting yellow precipitate is filtered off and in 1000 parts of water with a Content of about 10 parts of aqueous sodium hydroxide of 50 ° Be * suspended. The slurry will last about 90 hours left to stand and then filtered. The filter residue is dissolved in about 160 parts of acetone and the solution is poured into about 1000 parts of water. The resulting yellow semi-solid mass, which solidifies after about 16 hours of standing,

away
is filtered and ^{dried at 50 9} C in vacuo. This gave as pale yellow crystals of P «126-1281; (uncorrected) 7 parts of 2- (p ~ methoxyphenylarainovinyl) -5 »2-dimethylindoline of the formula i

009829/1799

-CH-CH-N

OCH,

Analysis: Ber. Qef.

N 9

The product let in methanol and similar alcohols of low molecular weight soluble. One drop of a 1 ^ (pale yellow) alcoholic solution calls filter paper impregnated with succinic acid immediately an intense yellow color.

Example 2 The procedure is as described in Example 1, with the Modification »dae instead of indoline-2-acetaldehyde

10.65 parts of 3,3-dimethylindoline-2-crotonic aldehyde are used will. The yellow product obtained is 2- (p ~ methoxy phenylimlno-2-butenediylidene) -3, ^ - dimethyl-indolln der Formula:

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-CH-CH-CH-N-

OCH,

A long (yellow colored) alcoholic solution of this Compound gets impregnated with succinic acid Filter paper shows an intense yellow color.

Example 3 It is discolored, as described in Example 1, with the Modification that instead of indoline-2-acetaldehyde

11.95 parts of 3,3-diethylindoline-2-8orbaldehyde are used will. The reddish yellow product obtained is 2- (p-methoxy phanyliinino-2, * -hexadileiKHyliden) -3,3-diyn «thylindoline the formula

Φ *

C ^ H-CH-CH-CH-CH-CH-H

A (reddish-yellow colored) 1 yuan alcoholic solution this connection calls for a «succinic acid-impregnated filter paper · intensive · Orange color.

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1645cfO5

Example 4

Instead of the p-anisidine in Example 1, 4.65 Aniline used. The corresponding itnino compound of the formula is obtained

A drip ^ js one (mhi? M & kmmk yellowbf ^ -fapfefe alcohol isslien Xjösuiig almmv ¥ ®irMsiÄKiig yuft on a with

getx ^ iikteia Pilftsg ^ spie ^ © in © ag.

Instead of de? 3 "3-X>lnethylindolifö-S-ald" lisrde and the arylamines " as used in ύ @ η ebigpn examples also know andss ¹ ^ suitable ^^ - disubstituted xndoline-2-aldehydes and priffiMx'e arylamines can be used, e.g. those contained in the list above. Instead of the aldehydes, the corresponding acetals or other aldehyde precursors or the corresponding methylene dichlorides or methylene dihromides can also be used.

Next you can use the new connections instead of the one above called way also by condensation of the corresponding

009829/1799

2-Methyl-2,3-di-substituted en-indolines with secondary ones Arylamine. that a suitable OxoalkyΙο the corresponding group is deceptive as the N-substituent and that with this group to a polymethine compound of the type mentioned above, preferably under the influence of an acidic catalyst or condensate and react in a suitable solvent.

When brought into contact with an acidic electron acceptor The new compounds give deep colorations in the yellow to red part of the visible spectrum, in this way Is the color range within which colorations are achieved with chromogenic tin-electron donor compounds can cover the entire visible spectrum from blue to red been expanded. In addition, the compounds of the present invention also enable the preparation of black colorations by using the red and yellow electron-donating chromogenic compounds of this invention with suitable known chromogenic electron donor compounds which, when combined with acidic electron acceptors, give blue to green colorations, in suitable Mixes proportions.

As indicated above, the 2,3-dl-substituted indolines of the present invention are good for use as the electron donor component of the "colorless carbon papers ^11"

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suitable that when applying pressure to the

Print spots show color formation. Accordingly

the present invention also encompasses pressure sensitive ones

Reproduction materials used as electron donor Component a 3i3-dl-substituted indoline as above

has been described. These indolines can be used in any any of the types described below are pressure sensitive

Paper, using known methods, e.g.

that in U.S. Patents 2,505,470; 2,548,566 2,618,573 and British patents 788,427, 8o4 087 and 835 930 and the German application A 45 471 VIb / 15q described by the same applicant if you look at the there mentioned electron donor compounds by those of present invention replaced, introduced throw.

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Claims (1)

1645Ü05 Claims 1. 2- (arylamino-polymethine) -3,3-disubstituted free of ionizable hydrogen-containing groups Indoline, characterized « that the Polyraathinrest is a conjugated chain from a even «10 not exceeding number of carbon atoms, which has a double bond at each end and via the double bond at one end to the nitrogen atom of the arylamino radical and via the double bond is bonded at the other end to the Cg atom of the xndole nucleus, the nitrogen atom of the indoline nucleus to sin Hydrogen atom is bonded. 2. indoline according to claim 1, characterized draws "that it has the following formula: R ^{1 1} »2 (-CH-CH) _n -HA 009829/1799 NtWi Unttriteen in which R is halogen, nitro, alkyl, alkoxy, »cycloalkyl, aralkyl, aryl, alkylsulfonyl, arylsulfonyl or sulfenyl 1st, R and R are halogen, alkyl, cycloalkyl, aralkyl or aryl, χ Ο or an integer from 1-4, N is an integer count of 1-5 and a is a hydrogen-containing groups of ionizable free aryl group. 3. A method for producing an indoline according to claim 1, characterized in that a 3,3-disubstituted which is free of ionizable hydrogen Indoline, which carries the reactive group in 2 digits, with an arylamino compound free of ionizable hydrogen, which can bond with the named reactive group to form the named ";" polymethine residue, implements. 4. The method according to claim 3s, characterized in that that one is a compound of the formula 009829/1799 905 with a compound of the formula .Y-N-A 1 2
in which R, R, R, χ and A have the meaning given in claim 2 and Q and Y are radicals which are mutually interconnected to form a radical (-CH-CH) _n **, which is the C ₂ atom of j3> J5-disubstituted indoline radical connects with the radical = NA, can react, and η is an integer from 1-5, converts. 5 «Method according to claim 4, characterized in that Q is = CH-CHO or CHC ^ GH = CH) _n -CHO, wherein η is an integer of 1-4, with and Y Hg means. 6. The method according to claim 5 # characterized in that the reaction in the presence of an acidic Condensation medium is carried out. ?. Verfrihren according to claim 6, since ä u raw ge "■ ks η η 7, s t-1 ch η e, that the reaction at a temperature of |? 0 - 25O ⁰ C in an inert liquid iiedium executed WAR S. 009829/1799 BATH 8. Use of an indoline according to one of claims 1 and 2 as an electron donor component of a pressure sensitive reproductive material. 009829/1799