DE3019248A1 - METHOD FOR (ALPHA) -CHLORINATING A SIDE CHAIN OF AN AROMATIC COMPOUND - Google Patents

Description

iPR-INCWALTERABITZ ^ο - ^ν "- ^Λ " ^{: 2} ° · ⁵

Tm. DIETER F. MORF Ji> IPL.-PHYS. M. GRITSCHNEDER

Poitanachrtft./ Postal Addr ·· « FienzanaueritraC 28 t

Telephone «83323

l> ltgr "mm": Chemlndu "Munich Telex: (O) 833003

CR-7866

E. I. DUPONT DE NEMORS AND COMPANY 10th and Market Streets, Wilmington, Del. 19898, USA

Process for the αΛ-chlorination of a side chain an aromatic compound

"S.

13Q048 / 031 *

E.I, duPont de Nemours and Company

CR-7866

description

The present invention relates to an α-chlorination process with dichloro-ion oxide / which in the literature is often called chlorine monoxide referred to as.

Chem. Rev. 7JL '4 £ J7 (1976) describes reactions of chlorine monoxide described with various organic compounds.

US Pat. No. 3,872,176 describes the production of 1,1,1-trichloroethane by, reaction of chlorine monoxide with chloroethane or 1,1-dichloroethane described.

In none of these references is the α-chlorination a side chain of an aromatic compound.

The present invention relates to a process for the α-chlorination of a side chain of an electronegatively substituted one aromatic compound of the general formulas I to V with dichloromonoxide (CL-O):

CHR ¹ R

(CHR'R ") _b (R'R" CH) _c 0

II

III

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where in the general formula I:

X stands for NO ₂ , CN, CF ₃ , BR, F, CR ₁ ,

Il

SO ₂ CF ₃ , SO ₂ Cl, SO ₂ NR ₃ R ₄ , OCR ₅ ,

O 0

NR ₆ CR ₂ , P (R ₂ ) ₃ , P (OR ₂ ) _2, or CCl ₃ ;

O Y stands for H, NO ₉ , Cl, Br, F, CN, CF-, CR ₁ , SO ₀ R ₀ ,

• Cm JI Al jL

O SO ₃ Fi ₂ , SO ₂ NR ₃ R ₄ , OCF ₃ , OCR ₅ , OR ₆ or aryl;

Z stands for H, Cl or B ^ - and in the general formulas II to V:

X ¹ and X ² independently of one another represent

SO ₂ CF ₃ / SO ₂ Cl, SO ₂ NR ₃ R ₄ , OCR ₅ , N (R ₂ ) ₃ ,

"OQ '·

11. .1. - 11.

NR ₆ CR ₂ , P (R ₂ J ₃ , P (OR ₂ ) ₂ or CCl ₃ or in the; general formula III also for hydrogen;

Y ¹ and Y independently of one another stand for

0 H; NO ₂ , Cl, Br, CN or CR ₁ ; and

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in the general forms in I to V:

ΤΗ stands for alkyl with 1 - 8 carbon atoms, aryl,. ,

Alkoxy with 1 - 4 carbon atoms, OH or

R stands for alkyl of 1-4 carbon atoms;

3 4

R and R independently of one another represent H or

Alkyl of 1-4 carbon atoms;

R stands for alkyl with 1-8 carbon atoms, trifluoro- " . methyl or aryl; f

6 ■ ·

R stands for H or alkyl with 1 - 3 carbon atoms,:

and · · :

R 'and R "independently represent H,

Alkyl with 1-3 carbon atoms or together form a carbocyclic ring with 5-6 carbon atoms; and R "also stands for alkyl having 1 to 20 carbon atoms ;

R "', R and R independently of one another represent H or Methyl;

R and R independently of one another represent H, alkyl ■ with 1 - 3 carbon atoms or together form a carbocyclic ring with . 5-6 carbon atoms;

a is 0 or 1;

b and c are independently 1 or 2;

/ ■

η means 1 or 2; d means 0, 1 or 2, and m means one! Number from 0-6 ,. with the proviso that,

CR-7866

when X is NRgCOR ₂ , then Y and Z cannot both be H, and that when Y is 0R _g , Z cannot be H.

The general formula II is to be understood such that X and Y on the same ring or on different rings can, and that for the cases in which b has the meaning of 2, each of the two identical CHR'R "residues also am the same ring or on the different rings.

For a narrower group of et-chlorinated compounds the general formulas. I-V have the individual symbols the following meanings:.

In general formula I:

X stands for NO ₂ , "Cl, Br, CN, CF ₃ , CR ₁ , - SO ₂ R ₃ , SO ₃ NR ₃ R ₄ ,

0 O

Il Il ' ■ - -' ■

SO ₃ R ₃ , OCR ₅ , NR ₆ CR ₃ or CCl ₃ ;

0. ■ -; ■■

Il

Y stands for H, NO-, Cl, Br, CN, CF. ,, CR ₁ , SO ₁ R, or OR- ·;

Z represents H, Cl, or Br; and -. - .- ■

in the general formulas II - V:

X and X independently of one another represent I.

^J NO ₂ , Cl, Br, CN, CF ₃ , CR ₁ , SO ₃ R ₂ , SO ₂ NR ₃ R ₄ ^,! 0 0

ft Il

SO ₀ R ₀ , OCR_, NR ^ CR- or CCl ₀ or in the general formula III are also hydrogen;

1 2 · "■ '

Y and Y independently of one another represent H, NO ₂ , CL

or Br; and

R-R, a, b, c, s d, η and m have those specified in claim 1 Meaning; and

R ', R ", R and R independently of one another stand for Hydrogen or alkyl of 1-3 carbon atoms; and

R "', R and R independently of one another represent hydrogen or methyl.

For an even narrower group of ot-chlorinated compounds the individual symbols in the individual forms have the following meanings: j

In general formula I:

O,

X represents NO ₂ , Cl, Br, CN, CF ₃ , CR ₁ , SO ₂ R ₃ , SO ₂ NR ₃ R ₄ ;

Il - "

or OCR ₅ ; ,

Y stands for H, NO ₂ , CL or Br; Z represents H, Cl, or Br; and

in the general formulas H-V:

12th X and X stand independently of one another for

0 NO ₂ , Cl, Br, CN, CF ₃ , CR ₁ , SO ₂ R ₃ , SO ₃ NR ₃ R ₄

or ^oeR 5 or in the general formula III they also mean hydrogen;

T 2

Y and Y are, independently of one another, H, N0 ~, Cl

or Br; and

R ₁ represents alkyl with 1-8 carbon atoms, aryl or alkoxy with 1-4 carbon atoms;

R ₂ represents alkyl of 1-4 carbon atoms;

R ₃ and R. independently of one another denote alkyl with

^CR ~ ⁷⁸⁶⁶ .30192 A

1-4 carbon atoms;

R _r stands for alkyl with 1-8 carbon atoms or aryl; j R stands for alkyl with 1-3 carbon atoms ;.

R ', R ", R and R independently of one another represent H or alkyl having 1-3 carbon atoms;

R " ¹ , R and R independently of one another represent -H or methyl;

a is 0 or 1; .

b and η mean 1 or 2,

c is equal to 1;

d is 0 or 1;

in means a number from 0 to 6.

In the case of an even more restricted group of oil- chlorinated compounds, the individual symbols have the following meanings.

In general formula I:

¹ O
X stands for NO ₃ , Cl, CN, CP ₃ , CR ₁ or SO ₂ RY stands for H, NO ₂ or Cl;
Z represents H or Cl; ·

R ₁ stands for alkyl having 1-8 carbon atoms, aryl or alkoxy having 1-4 carbon atoms;

R ₂ represents alkyl of 1-4 carbon atoms;

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R ¹ , R ″, R and R independently of one another represent H or alkyl having 1-3 carbon atoms;

IV V
R "', R and R independently of one another mean H or

Methyl;
a is equal to 0 or 1;

with the proviso that X has the meaning of NO-, Cl or CN when a = 1, Z = Cl and Y = NO ₂ or Cl.

The inventive method relates to the chlorination with Dichloromonoxide to achieve α-chlorination of a side chain of an electronegatively substituted aromatic compound / with the proviso that the net effect of the substituents on the aromatic is electron withdrawing. The estimate or determination of the electron withdrawing character is known and can be done using Hammett's σ constants according to the teachings of L.P. Hammet, in Physical Organic Chemistry, McGraw-Hill, 2nd Edition, 1970, Chapter 11, or by linear combination of the σ ..- (polar effects) and σ (pi-delocalization effects) constants according to the teachings of S. Ehrenson, R.T.C. Brownlee and R.W. Taft in Prog. Phys. Org. Chem., J_0, 1 (1973), A. Streitwieser, Jr. R. W. Taft, (Eds.), John Wiley and Sons, N.Y. or M. Charton, in Prog. Phys. Org. Chem. 8 ^, 235 (1971).

In the context of the present invention, "α-chlorination" means the substitution of at least one hydrogen atom by a'Chloratom on a saturated hydrocarbon atom, the is in the immediate vicinity of the aromatic ring. An "α-hydrogen atom" is such a hydrogen atom to understand the thing about this saturated hydrocarbon atom stands. ·

In the context of the present invention, a "side

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chain "one through a saturated carbon atom to which at least one hydrogen atom is present to an aromatic one The radical bonded to the core. The side chain can be straight-chain or branched, or it can contain a cyclic group or be connected to the aromatic nucleus at another point.

Particular examples of compounds suitable for the α-chlorination are those of the general formulas I to V, as defined above. -. - ·

It has been found that the α-chlorination of a side chain of an electronegatively substituted aromatic compound normally proceeds in high yields by using dichloromonoxide. The chlorination is extremely selective and, often associated with quantitative yields, and little or no by-products are obtained in which chlorination occurs of the nucleus or other positions occurs. The reactions are gradual reactions in which the chlorine atoms are sequential are introduced, and therefore leads to the use of inadequate Dichloromonoxide or stopping the reaction before it is complete to any products that That is, to those products that are partially or completely attached to the saturated carbon atom, which is the aromatic nucleus is adjacent are chlorinated. With some ortho-substituted aromatic compounds, such as substituted o-xylene compounds, may be incomplete substitution of all α-hydrogen atoms occur through Shloratome, which on steric factors. The extent of the chlorination can suitably be followed by HNMR spectroscopy and other analytical spectroscopic methods and be determined.

In the inventive α-chlorination process of aromatic Compounds, the aromatic compound is reacted with dichloromonoxide .., which of the reaction is gaseous or is supplied in solution.

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Because of the extremely oxidative nature of dichloromonoxide, it is necessary to dilute the chlorinating agent in order to eliminate the risk of explosion. A diluent gas is usually used for this purpose if dichloromonoxide is to be added in gaseous form, and the type of addition can vary widely, usually the diluent gas should be inert or essentially inert with respect to the cL chlorination in order to avoid the introduction of by-product impurities . Air, nitrogen and argon can be used as diluent gases, air being preferred for reasons of cost. A suitable molar ratio of diluent gas to dichloro monoxide is in a range from 1: 1 to 500: 1. Lower concentrations of diluent can also be used, but the risk of explosion increases if the concentration of diluent is significantly reduced. Furthermore, higher concentrations of diluent than indicated above can also be used.

As an alternative to this, the dichloromonoxide can also be added to the reaction in a solvent. A large number of solvents can be used, including carbon tetrachloride, acetonitrile, methylene chloride, chloroform, trichlor fluorine than, 1,2-dichloro-1,1, 2,2-tetrafluoroethane and 1-chlorotetrafluoroethane. Acetonitrile, methylene chloride and chloroform can _{react slowly with Cl 2} O, but they are suitable solvents for rapid reactions. A preferred solvent is carbon tetrachloride. The concentration of dichloromonoxide in solution is not critical. High concentrations of dichloromonoxide lead to faster deterioration when stored for a longer period of time, which is due to the reduction in half-life.

For the α-chlorination, the dichloromonoxide is either in the gas phase or in solution with the aromatic defined above Connection implemented. The aromatic compound can be mixed directly in the solid or molten state with the dichloro monoxide,

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which is diluted with a carrier gas or a solvent is to be converted for chlorination. Alternatively, this can the aromatic compound can also be used in the form of a solution by using a solvent. The type of Solvent depends on the aromatic Ver ^ to be converted binding and can vary widely * If that Dichloromonoxide is also used in solution, it is not necessary, the same solvent for the aromatic compound to choose. There is therefore one choice of a suitable solvent for each reactant great flexibility.

The temperatures which may be employed in the α-halogenation, may vary within a wide range, such as within -50 ⁰ C to 250 ⁰ C, preferably 0 ° C to 150 ⁰ C. The pressure is not critical since pressures above - and can be used below atmospheric pressure. For the sake of simplicity, an atmospheric pressure or a pressure slightly above atmospheric pressure is preferred. When using a solvent, it is evident that the combination of temperature and pressure should not result in rapid evaporation of the solvent or dichloromonoxide. If the aromatic ring is not severely deactivated by electron withdrawing groups, the A-chlorination occurs rapidly and therefore lower temperatures are preferred, at least in the initial stages of the reaction, in order to prevent the formation of by-products. If the organic ring is heavily deactivated by electron withdrawing groups, the reaction generally proceeds more slowly and accordingly higher temperatures, longer reaction times or catalytic acceleration by light are required.

If all available α-hydrogen atoms are to be substituted ", an excess of dichloromonoxide is used. For an optimal product yield, product purity and the shortest possible reaction time, an excess of Cl ₂ O is suitably used, especially when the aromatic mixture

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binding is strongly deactivated by electron withdrawing groups.

The response time can be a few minutes to a few days. The reactions are not noticeably inhibited by air, small amounts of chlorine or conventional radical inhibitors. The reactions are catalyzed by diffuse light and by strong light, such as by a mountain sun, noticeably accelerated. Usually the presence of excess dichloromonoxide does not lead to an increase Formation of by-products. However, if the reactions are catalyzed by exposure to strong light, excess can occur Dichloromonoxide lead to the formation of by-products, which is presumably due to substituent exchange reactions.

In general, water is the main by-product of the reaction, and its concentration in the reaction zone is usually kept to a minimum. Excess water hydrolyzes-Cl-Q-in an equilibrium reaction with the formation of hypochlorous acid:

Cl ₂ O '+ H ₂ O * 2 HOCl.

In the case of a water-immiscible reaction system, the water is automatically separated off from the reaction zone in the form of a discrete second phase, and the equilibrium reaction therefore promotes the formation of _{Cl 2 O.} The separation of water from the reaction zone by mechanical means, inert drying agents such as calcium nitrate, or by azeotropic or conventional distillation in this way favors the more effective use of Cl ₂ O. The presence of excess water and longer reaction times can also lead to the hydrolysis of the chlorinated products under formation ^; of ketones, acid chlorides or acids.

The electronegatively substituted aromatic compound with a side chain for α-halogenation is the starting material

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material in the inventive method. Many of these Compounds are commercially available or can be based on known ones In a manner familiar to those skilled in the art.

The starting materials are either known or are after can be produced using the processes described in the literature, as described, for example, in:,

(1) "Rodd's Chemistry of Carbon Compounds, 2nd Edition,

S. Coffey. (Eds.), Volume III, Elsevier Publishing Company, 1971

(2) "Principles of Organic Synthesis", R.O.C. Norman, Methuen and Co., Ltd., London 1968.

(3) "Aromatic Nucleophilic Substituion", J. Miller, Elsevier Publishing Company, 1968.

(4) "Electrophilic Substituion on Benzenoid Compounds", R.O.C. Norman and R. Taylor, Elsevier Publishing Company, 1965.

(5) "Friedel-Crafts and Related Reactions", GA Olah _t (Ed.), Interscience Publishers (J. Wiley and Sons), 1963.

(6) "Aromatic Substituion, Nitration and Halogenation", P.B.D. de la Mare and J.H. Ridd, Butterworths Scientific Publications, 1959.

The invention using dichloromonoxide as Α-Chlorinated compounds produced by chlorinating agents are widely used. These α-chlorinated compounds are often intermediates, although some of these compounds can be used directly without further reaction. The α-chlorinated compounds are suitable as intermediates in the production of agricultural chemicals, such as for example insecticides and fungicides, pharmaceuticals, antistatic agents, flame retardants, surface-active agents, oil additives, fuel additives, lubricants, elastomers and plasticizers.

Benzotrichlorides react with activated aromatic compounds in aqueous HF with formation of benzophenones. Benzophenones, such as 2-chloro-5'-t-butyl-2'-hydroxybenzophenone, are active insecticides (Chemical Abstracts 40: 1251c), and 4-chloro-4'-phenoxabenzophenone is according to the

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German patent application 24 51 037 a suitable PVC plasticizer. In this patent application there is also a UV stabilizing property of 4-chloro-2'-hydroxy-4'-methoxybenzophenone described, and it is further disclosed there that related benzophenones are suitable metal complexing agents, Metal extractants, dyes, and pharmaceuticals are.

As an example of α-chlorinated compounds where available standing α-hydrogen atoms by monochlorine exchange have been replaced, the production of intermediate products stands. For example, DE-OS 26 59 404 discloses that compounds such as 3-chloro-βj a-dimethylbenzylamine, which is made from S-chloro-aja-dimethylbenzyl chloride can be obtained by the process according to the invention, are suitable for the production of selective herbicides.

As an example of α-chlorinated compounds where available standing a-hydrogen atoms by dichloro exchange have been replaced, comes the manufacture of intermediates for use as bactericides and fungicides according to US Pat. No. 3,457,310.

As an example of α-chlorinated compounds where available standing «hydrogen atoms through trichloro exchange have been substituted (on a single carbon atom), the manufacture of intermediates for bactericidal and fungicidal purposes can be mentioned, as is the case for example in U.S. Patent 3,457,310 for compounds such as 4-chloro-3-trichloromethylbenzotrifluoride. 1,4-bis (trichloromethyl) benzene and related compounds are, according to US Pat. No. 3,663,710, valuable compounds in the improvement the conversion of feed in ruminants.

The following paragraphs serve to explain the special application possibilities of α-halogenated compounds, the have been produced in accordance with the process of the invention.

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Benzotrichlorides prepared according to the invention are valuable Intermediate products in the manufacture of agricultural chemicals. An example is 4-chloro-3,5-dinitrobenzotrifluoride an intermediate product involved in the manufacture of Herbicides such as trifluralin is used (U.S. Patent 3,257,190). According to the British patent specification

1 455 207 finds 4-chloro-3-nitrobenzotrifluoride used as Intermediate product in the manufacture of the mite control agent fentrifanil.

Ring halogenated benzotrifluorides such as 2,4,5-trichlorobenzotrifluoride have dielectric properties, which makes them are useful isolating agents and converting fluids (U.S. Patent 2,063,979).

Nitrobenzotrifluorides, such as 3,5-dinitro-2-chlorobenzotrifluoride, are valuable compounds in the preparation of azo dyes according to US patents

2,194,925 and 2,212,825. G. Hailas and J.D. Describe Hepworth in the Journal of the Society of Dayers and Colourists, 86, 200 (1970) that malachite green-related dyes from 1,3-bis- (trifluoromethyl) -benzene can be produced.

2-chloro-7-trifluoromethylanthraquinone can be mentioned as an example of anthracene dye intermediates which can be obtained by the process according to the invention ( J. H. Simons, ed., Fluorin Chemistry, 248-253, Academic Press, 1965, New York) .

According to British patent 813 861, nitrobenzotrifluorides, such as 3-nitrobenzotrifluoride, useful intermediates in the manufacture of pharmaceuticals such as the important tranquilizer Trifluoperazine.

DE-OS 25 41 752 discloses that 2-carbomethoxy-5 (6) - (3-trifluoromethylphenylsulfonyloxy) benzimidazole, a from 3-trifluoromethylbenzenesulfonyl chloride preparable

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. 301924a

binding, which is a useful wormer.

Trifluoromethylphenylphosphonic acid dihalides obtained from according to the invention manufacturable inventions are available as intermediates for flame retardants in the Dutch patent application 7 214 241 described.

Intermediate products for polymers, such as 3-trifluoromethylstyrene, obtainable from compounds which can be prepared according to the invention are available from G.B. Bachman and L.L. Lewis and polymerized (J.Am.Chem.Soc. jjjJ, 2022 (1974)).

According to U.S. Patents 3,813,446 and 2,442,345, Azo dyes, such as 2-methyl-7- (trifluoromethyl) benzomorpholine, made from 4-chloro-3-nitrobenzotrifluoride will.

The following examples serve to illustrate the invention, however, they do not limit them. Unless otherwise stated, all temperature data are in degrees Celsius specified.

Unless otherwise noted, analyzes were performed using nuclear magnetic resonance spectroscopy on a Varian A60 and with the aid of a high-resolution liquid chromatography process (HPLC) using a 50 cm 4.6 mm ID column, filled with a porous, microspherical silicon dioxide adsorbent (Particle size 7μ, pore diameter 74A, pore volume 547 cc / g), the elution with 0.1 to 0.3% methanol in isooctane at a pressure of 110.3 bar (1600 psi) and a flow rate of 1.54 ml / min. The fractions were determined with an ÜV detector (254 ran).

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ZH.

example 1

+ 3 Cl ₂ O r * 2

CCl.

A Hastelloy pressure tube is flushed with nitrogen and filled with p-nitrotolupl (20.9 g, 0.152 mol) and dichloromonoxide (29.14 g, 0.335 mol) dissolved in carbon tetrachloride (450 ml). The solution is heated to 75 ° C. under autogenous pressure for 8 hours. The water layer is separated and the organic layer is dried (MgSO ₄ ). The solvent is stripped off using a rotary evaporator, and an almost colorless oil is obtained which solidifies to a white solid on standing (36.83 g, purity according to HPLC 99.27%, yield 100%). By comparing its HNMR and IR spectra and its retention time in high pressure liquid chromatography with those of an authentic sample, the product is identified as i-nitro-4-trichloromethylbenzene. The product can be recrystallized from petroleum ether (boiling point 35.8 to 56.5), and an almost pure product with a melting point of 45.8 to 46.9 ° C. is obtained.

HNMR 6 ^CDC1 3

e ^CH 3 ^CN =, 189
350

e ^CH 3 ^CN = 11,900
259

8.2 AB quartet (aromatic protons)

-.16-

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Example 2

+ 3

CCl.

A one-necked flask is flushed with nitrogen and then filled with p-nitrotoluene (33.30 g, 0.24 mol) _r carbon tetrachloride (30 ml) and dichloromonoxide (42.41 g, 0.486 mol) dissolved in carbon tetrachloride (75 ml) . The flask is closed with a stopper and stored at room temperature. The solution quickly becomes cloudy and a layer of water separates out. After 96 hours the brown color of the chlorine monoxide has disappeared. The water layer is separated off and the solution is filtered to separate off the p-nitrobenzoic acid (0.83 g). The piltrate is dried (MgSO ₄ ) and the solvent removed in a rotary evaporator. A pale yellow, crystalline solid is obtained (58.80 g, degree of purity according to HPLC 99.05%, yield 99.75%), which by comparing the IR and HNMR spectra with an authentic sample as i-Nitro-4- trichloromethylbenzene is identified,

Example 3

+ 3 H ₂ O

p-Nitrotoluene (1.03 g, 0.0075 mol) and dichloromonoxide (2.5 g, 0.0285 mol) in. Carbon tetrachloride (48.5 ml) are in put into a dry single-necked flask, which is then

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is closed. A 275 W sunlamp is about 30.5 cm (12 ") above the flask. After 1.5 hours, the reaction mixture is dried and the solvent in withdrawn from a rotary evaporator. A pale yellow oil (1.96 g) is obtained which, according to HNMR analysis and gas-liquid chromatography unreacted p-nitrotoluene (3.32%) p-nitrobenzyl chloride (5.15%), p-nitrobenzal chloride (24.87%) and 1-nitro-4-trichloromethylbenzene (64.86%) 'contains. By a similar reaction lasting 6.9 hours is obtained crystalline solid (2.02 g) derived from i-nitro-4-trichloromethylbenzene (84.37%) and a mixture of by-products (15.67%), most of which are presumably due to exchange reactions the nitro and / or the -CCl., - groups and are due to ring substitutions.

A similar reaction, carried out in normal room lighting, takes about 18 hours to produce 1-nitro-4-trichloromethylbenzene (97.3%). If another similar experiment was carried out in complete darkness, it would take 94 hours to obtain a product that Contains 88.2% i-nitro-4-trichloromethylbenzene.

Example 4

■ »2

+ 3 H ₂ O

p-Nitrotoluene (1.03 g, 0.0075 mol) and dichloromonoxide (1.37 g, 0.016 mol) in carbon tetrachloride are intimately mixed. The solution is divided into three equal parts and each part was heated in a Carrius tube at 75 ⁰ C. After the reaction times given below, the product is dried and the solvent is stripped off in a rotary evaporator.

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The HPLC AnaIyse yields the _(following values:

Time
(Hours.)

product

(G)

1.88 1.86 1.87

0.10

0.29

1) p-Nt = p-nitrotoluene

2) p-NBCl = p-nitrobenzyl chloride

3) p-NBCl ₂ = p-nitrobenzal chloride

4) P-NBCl ₃ = p-nitrobenzotrichloride

2.52 0.07 0

97.3fi 99.93 100

Example 5

+ HgO + Cl,

. NO

CCl.

CHCl.

Yellow mercury oxide (19.8 g), p-nitrotoluene (6.0 g, 0.044 mol) and carbon tetrachloride (180 ml) are stirred and heated to reflux while adding chlorine (10 g) for about T hour. Heating under reflux conditions is carried out for a further 2.5 hours, and the mixture is then at room temperature for 6 days long stirred. The mixture is filtered and the solvent removed from the filtrate in a rotary evaporator, and an almost colorless oil (9.85 g) is obtained, which, determined by comparing its HNMR spectra and its HPLC retention times with those of authentic samples, a mixture of p-nitrotoluene (1.99%), p-nitrobenzyl chloride (3.95%), p-nitrobenzal chloride (17.88%) and 1-nitro-4-triehlomethylbenzene (76.19%) contains.

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Example 6

301924?

2

CCl

+ y

m-nitrotoluene (3.55 g, 0.026 mol) and dichloromonoxide (4.72 g, 0.054 mol) in carbon tetrachloride (75 ml) are poured into a Carrius tube given. The air is removed and the mixture is heated to 75 ° for 6.75 hours. The product is dried (MgSO.), And the solvent in a rotary evaporator deducted. An almost colorless oil (6.78 g, Degree of purity according to HPLC: 96.79%, yield 100%). This Product is combined with the product of a similar approach and stored in a short-path distillation device (bath 95-100 / 0.1μ) distilled, and one obtains an analytically pure

nes product (Ν _β 1, 5762) • 5 N 0 44 Cl Elemental analysis for C ₇ H ₄ NO ₂ Cl ₃ : 6th , 82 13.31 44 , 23 C. H xe , 07 Dmat. , 25 calculated 34 , 96 1.68 NS Doe (arc isc found 35 , 32 1.96 CDf "! / Ψ
HNMR 3 'Λ 7 .69-8.88 komole

JT - 3.23μ, 3.42μ (trace, saturated CH) weak 5.77μ

(> C = 0 impurity); 6.20µ, 6.32µ (aromatic C = C); 6.55μ, 7.45μ (NO-)

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Example 7

CCl.

CHCl.

3019240

CCl.

HCl.

4-o-Nitroxylene (1.95 g, 0.013 mol) and dichloromonoxide (4.72 g, 0.0543 mol) are heated to 75 ° in a Carrius tube for 6.75 hours and then according to the method described in Example 6 treated. The product is dried (MgSO ₄ ) and the solvent removed. Pale yellow crystals are obtained. The HPLC analysis shows that the product consists of a mixture of two compounds (47.80% and 48.86%.) And minor amounts of various impurities. By HNMR analysis, the products are identified as 1-nitro-3-trichloromethyl-4-dichloromethylbenzene and 1-nitro-3-dichloromethyl-4-trichloromethylbenzene.

HNMR ^CDC1 3 ^{/ T} δ

7.79 TH singlet (CHCl ₂ ) δ 8.22-8.50 2H complex (aromatic protons) δ 8.95 1H complex (aromatic protons)

In the 220 HNMR spectra, the 7.79 singlet becomes two Singlets of approximately the same size or weight split up. The other two complex groups are each split into two complex groups of equal size or equal weight split.

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Example 8

+ 3

5-nitro-m-xylene (2.15 g, 0.014 mol) and dichloromonoxide (6.79 g, 0.078 mol) in carbon tetrachloride (70 ml) are as described in Example 6 in a Carrius tube for 18.5 hours Heated to 75 °. The product is dried (MgSCK) and the solvent removed in a rotary evaporator. A pale yellow oil is obtained (5.46 g, degree of purity according to HPLC: 99.70 yield 100%). The oil is distilled in a short-path distillation device (boiling point *> * 115 / 0.5 mm), and a pale yellow oil is obtained.

Elemental analysis for CgHoNO-Clg:

26th C. 0, H 3 N 8th O 59 egg calculated 27 , 85 1, 85 3 , 91 , 94 59 , 45 found , 39 12th , 99 , 42

mn / τ

HNMR 3 'δ 8.83 singlet (aromatic protons)

jr ^KBr 3.22µ (= CH); 6, 18μ (aromatic C = C bond)); 6.47μ,

7.44μ (NO ₂ ) multiple bands at 12.5μ (CCl ₃ )

_ 22 -

130048/0312

CR-7866

Example 9

2

301924a

■ + 3 H ₂ o

2-chloro-4-nitrotoluene (2.19 g, 0.0128 mol) and dichloro monoxide (4.46 g, 0.0513 mol) in carbon tetrachloride (50 ml) Heated to 75 ° for 18 hours and then according to that in Example 6 Process described worked up. The product is dried and the solvent removed and obtained i-Nitro-S-chloro - ^ - trichloromethylbenzene (3.49 g, purity according to HPLC 99.4 0%, yield 99.2% ■) in the form of a weak yellow oil, the product is in a short path still distilled (boiling point 82-85 / 2μ) and a pale yellow oil is obtained.

Elemental analysis for C ₇ H ₃ NO ₂ Cl ₄ :

30th C. 1 H 5, N 1 O 51 Cl calculated 32 , 58 1 , 10 5, 09 1.64 48 , 58 found , 22 , 52 64 , 90

CDCl / T

HNMR y δ 8.5-8.8 complex group (aromatic protons) KBr

3.22µ (= CH); 6.53µ, 7.42 / * (NO ₂ ); 6.25μ, 6.30μ, 6.83μ (aromatic ^ C = C ^). Weak 5.85μ (> C = O contamination), long-wave multiple bands relating to CCl ₃ .

- 23 -

130 048/0 312

CR-7866

Example 10

3013248

+ 3

+ 3 H ₂ O

3,4-dinitrotoluene (2.49 g, 0.0136 mol) and dichloromonoxide (4.74 g, 0.055 mol) in carbon tetrachloride (50 ml) as in Example 6 in a Carrius tube from which the air has been removed, heated to 75 ° for 10 hours. The reaction solution is used to remove a white solid (0.35 g) filtered, which by means of IR spectroscopy as 3,4-dinitrobenzoic acid is identified. The Fi.ltr.at is dried (MgSO.) and the solvent removed in a rotary evaporator. I-Trichloromethyl-3,4-dinitrobenzene is obtained in the form of a white, crystalline solid (3.57 g, purity according to HPLC 96%, yield 89.2%). The product is recrystallized from carbon tetrachloride-petroleum ether, and a essentially pure product (melting point 69.5-70.6 °).

A portion is determined by preparative HPLC on a water's prep. 500 silica gel cartridge further cleaned. Eluting with acetonitrile (0.5%) butyl chloride (25%) and cyclopentane (74.5%) gives a white, crystalline solid with a Melting point of 70.3-71.4 °.

Elemental analysis for C-H ^ N-O.Clo:

29 C. 1 H 9 N 0 37 Cl calculated 29 , 45 1 , 06 9 , 81 22.42 37 , 26 found , 50 , 47 , 72 , 26

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130048/0312

CR-7866

CDCl / T
HNMR ■ 3 'δ 7.9-8.6 complex group (aromatic protons)

> ^KBr 3.22μ, 3.26μ (-OH): 6.45μ, 7.32μ, 7.43μ

Example 11

4-Äthylnitrobenzol (7.38 g, 0.052 mol) and Cl ₃ O (6.30 g, 0.073 mol) in carbon tetrachloride (75 ml), as described in Example 6, heated in a Carrius tube at 75 ⁰ C.

After 10 minutes the solution turns pale yellow, indicating that the reaction is essentially complete. Heating is then continued for a total of 8 hours. The product is dried (MgSO ₄ ) and the solvent removed in a rotary evaporator. A pale yellow, mobile oil is obtained from essentially pure 1- (1,1-dichloroethyl) -4-nitrobenzene (11.81 g) " which, according to HPLC analysis, has a degree of purity of 97 ^ 23% (yield 100% A portion of the product is distilled in a short-path distillation device (0.5μ, bath 100 °), and a pure product is obtained (N _D ²⁵ 1.5690).

Elemental analysis for CgH ₇ NO ₂ Cl ₂ :

calculated
found

43.66. 43.65

3.21 3.44

6.37 6.87

O
14.54

Cl

32.22 32.42

- 25 -

13004870312

CR-7866 HNMR ^CDC V ^T

301924a

5 2.58, 3H singlet (-CH ₃ )

6 7.78-8.35 4HAA ¹ BB ¹ specimen (aromatic

Protons)

^ _3/2 4 µ (= CH); 3.34µ, 3.41µ, 3.49µ (saturated CH); 6.22µ, 6.29µ (aromatic C = C); 6.55µ, 7.43µ (NO ₂ ) 7.25µ (C-CH ₃ ).

When repeating the experiment using a large Excess dichloromonoxide (molar ratio: 6/1) is obtained 1- (1,1-dichloroethyl) -4-nitrobenzene with a purity of 92.5% (HPLC) in a yield of 96%.

Example 12

. Cl

+ J

CCl.

p-chlorotoluene (1.17 g, 0.0092 mol) and dichloromonoxide (2.40 g, 0.028 mol) in carbon tetrachloride (35 ml) are mixed and in a flask closed with a stopper at room temperature Stored for 5 days. The initial reaction is exothermic. The product is dried (MgSCK) and the solvent stripped in a rotary evaporator. 4-chlorotrichloromethylbenzene is obtained in the form of a pale yellow oil (2.00 g, degree of purity according to HPLC analysis 88.78%, yield 83.9%), which contains a small amount of dichlorotrichloromethylbenzene contains.

HNMR

CDCl / T

3 'S 7.2-8.0 complex group (aromatic protons)

A subset of the product is in a liquid-gas chroma ⁱ tographiesäule separated (3% "sp2250" on 100-120 mesh Supel-

- 26 -

130048/0312

CR-7866

301924a

1.82 in (6ft) glass column, 75-250 ° at 4 ^ο / ΐτύη), the

coport,

The main product is eluted after 11.09 min and its mass spectrum is dur.ch identified as 4-chlorotrichloromethylbenzene (m 228). A smaller fraction, which is eluted after 13.10 min, is produced in the same way as dichlorotrichloromethylbenzene identified.

Example 13

+ Cl ₂ O

Methyl p-toluate (4.42 g, 0.0294 mol) and dichloromonoxide (6.40 g, 0.0736 mol) in carbon tetrachloride (75 ml) are according to the method described in Example 6 in a Carrius tube heated to 75 ° for 9.5 hours. The product will dried and the solvent in a rotary evaporator deducted. A white, crystalline solid is obtained which consists essentially of methyl p-trichloromethylbenzoate (7.93 g composition, according to HPLC 69.02%, yield 73.47%), and a small amount of chloromethyl p-trichloromethyl benzoate contains (7.93 g composition, 26.27% according to HPLC, yield 24.6%).

HNMR ^CDC1 3 ^ ^T 6 3.90 (-OCH.), 6 6.0 (OCH ₀ Cl), δ 8.0 (aromatic protons)

A portion of the product from a similar approach is separated on a gas-liquid chromatography column (3% ^u sp2250 "on -100-120 mesh Supelcoport, 1.82 m (6ft) glass column, 75 ° C-2'50 ⁰ C. at .4 ° / min) .. The main product is eluted after 24.32 min and, by its mass spectrum, as methyl p-trichloromethyl benzoate

- 27 -

130048/0312

CR-7866

identified. The fraction that is eluted after 30.38 min is made in the same way as chloromethyl p-trichloromethylbenzoate identified.

Example 14

+ 3

CCl.

+ 3

o-Tolunitrile (1.83 g, 0.0156 mol) and dichloromonoxide (6.79 g, 0.078 mol) in carbon tetrachloride are heated to 75 ° C. in a Carrius tube for 18.5 hours according to the method described in Example 6. The reaction mixture is dried (MgSO ₄ ) and the solvent is removed in a rotary evaporator. ^M to obtain a white crystalline solid (4.09 g, purity by HPLC 85.45%, yield 100%). The product is combined with that of a similar approach and recrystallized from cyclohexane. Substantially pure is obtained 2-Trichlormethylbenzonitril having a melting point of 98.9 to 100 ⁰ C.

Elemental analysis for CoH _{4 NCl 3} :

43 C. 1 H 6th N 48 Cl calculated 43 , 58 1 / 83 6th , 35 48 , 24 found , 86 , 88 , 17th , 30

CDf ¹ I / T-HNMR ^ ^X 3 ^X 6 7.23-8.32 complex group (aromatic protons)

3.22µ, 3.25µ (= CH) •; 4.47µ (CN); 6.28μ, 6.35μ, 6.77μ (aromatic C = C + bond), multiple bands for longer waves that are assigned to CCl ₃ .

- 28 -

130048/0312

CR-7 8.6 6

Example 15

301924a

+ 3

CCl.

H ₀ O;

p-Tolunitrile (4.10 g, 0.035 mol) and dichloromonoxide (6.93 g, 0.074 mol) in carbon tetrachloride (97 ml) are added to a flask under nitrogen. The flask is closed and stored at room temperature for 4 days. Separate the water layer, dry the organic layer (MgSO ₄ ) and remove the solvent on a rotary evaporator. P-Cyanobenzotrichloride is obtained in the form of an oil (7.87 g, yield 100%). The oil is combined with that of a similar approach and distilled in a short-path distillation device, giving a white, crystalline solid which is recrystallized from petroleum ether. Essentially pure p-cyanobenzotrichloride (melting point 40.5-41.7 °) is obtained.

Elemental analysis for CgH ₄ NCl ₃ :

calculated
found

C H N Cl

43.57 1.82 6.35 48.24

43.42 1.72 6.26 47.47

Mass spectrum;

measured m / e

218.9404 183.9730

calculated

218.9409
183.9721

Assignment

m-Cl

- 29

130048/0312

CR-7866

3.24μ (= CH), 4.48μ (CN), 6.24μ and 6.67 (aromatic C = C bond), multiple bands in the range of 12μ, originate from "CCl ₃ .

(TIPI

HNMR 3 δ 7.7-8.2 AA ¹ BB * sample

(symmetrical aromatic protons)

Example 16

+ 3

'Cl!

CCl.

3-chloro-4-methylbenzonitrile (3.52 g, 0.023 mol) and dichloro monoxide (6.05 g, 0.069 mol) in carbon tetrachloride (60 ml) are heated in a Carrius tube to "75 ° for 24 hours and the product is then isolated according to Example 3. A white, crystalline solid (4.0 g).

cnn / τ

HNMR 3 ⁷ ^ δ 7.59-8.42 complex group (aromatic protons)

+ 3

Example 17

> 2

CCl

CF.

+ 3

. - 30 -. . 130048/0312

3 t

CR-7866

1,1,1-trifluoro-p-xylene (2.78 g, 0.0174 mol) and dichloromonoxide (3.32 g, 0.038 mol) in carbon tetrachloride are in a Carrius tube for 14 hours according to the method described in Example 6 heated to 75 °. The product is dried (MgSO ₄ ) and the solvent removed in a rotary evaporator. A , α, α-Trifluor -— α ¹ , α ¹ , α '-triehlor-p-xylene is obtained in the form of a colorless oil (4.61 g, purity according to HPLC 88.40%, yield 89%). The product is dissolved in methylene chloride, washed with 6N NaOH, dried and distilled in a short-path distillation device (boiling point 36 ° / 1 mm). A colorless oil (3.0 g) is obtained.

Elemental analysis for C _n H-Cl ₃ F ₃ :

calculated found

C H Cl F

36.47 1.53 40.37 21.63

36.28 1.57 22.05

PDCl / T
HNMR- 3 'δ 7.73 AA ¹ BB ¹ pattern (aromatic protons)

-63.57 ppm, singlet (-CF ₃ )

6, 22μ (aromatic C-C bond) strong 7.5μ to 9.5μ

(C-F).

SO ₂ CH ₃

Example 18

-> 2

CCl.

- 31 -

13 004 8/0312

CR-7866

Methyl p-tolyl sulfone (4.40 g, 0.054 mol) and dichloromonoxide (4.72 g) in carbon tetrachloride (75 ml) are, as described in Example 6, in a Carrius tube for 6.75 hours Heated to 75 °.

Crystals precipitate on cooling to room temperature. That The product is filtered to separate the white crystals (5.99 g). The filtrate is dried and the solvent removed in a rotary evaporator, and additional ones are obtained Crystals (1.96 g). A portion of the product is recrystallized once from petroleum ether and pure one is obtained 1- (methylsulfonyl) -4- (trichloromethyl) benzene with a Melting point of 168-168.8 ° C.

Elemental analysis for C ₀ H ₇ SO ₂ Cl ₃ :.

C H S O Cl

calculated '35.12 2.58 11.72 11.70 38.88 35.17 2.64 Found _"-; 38.94.

HNMR ^CDC1 3 / ^T δ 3.12 3H singlet (CH ₃ )

δ .7.9-8.3 AA'BB 'pattern, symmetrical aromatic

Protons

_r ^KBr 3.25 µ (2CH); 3.35, 3.44 (saturated CH); 6.29µ (C = C aromatic bond); Multiple bands in the range of 7.75μ connected with 8.75μ (-SO ₂ ); Multiple bands in the range of 13μ (CCl ₃ ).

Mass spectrum:

measured.
m / e calculated 9232 Assignment 271.9264 271, 9543 C ₈ H ₇ O ₂ Gl ₃ S 236.9538 236, 9378 m-Cl 192.9404 192, In-CH ₃ SO ₂

- 32 -

130048/0312

CR-7866

Example 19

CCl

2,6-dichlorotoluene (1.49 g, 0.0092 mol) and dichloro monoxide (2.40 g, 0.0277 mol) in carbon tetrachloride (25 ml) heated according to the method of Example 6 in a Carrius tube at 75 ° for 20.3 hours. The product is dried and the solvent was removed on a rotary evaporator to give a pale yellow oil (2.84 g). The product is carried out on a gas-liquid chromatography column, as in example 12 described separately. Mass spectroscopic investigations of the main fractions show that the product consists mainly of 2,6-dichlorobenzyl chloride, with minor Amounts of 2,6-dichlorobenzal chloride and 2,6-dichlorobenzotrichloride and isomeric products are present, which can be attributed to ring substitutions.

Example 20

ci ₂ o

CHCl,

- 33 -

130048/0312

CR-7866

p-Methylacetophenone (1.98 g, 0.0148 mol) and dichloromonoxide (4.17 g, 0.0148 mol) in carbon tetrachloride (50 ml) are heated to 75 ° for 27 hours in a Carrius tube according to the method of Example 6 - heated. The product is dried and the solvent is removed in a rotary evaporator. A pale yellow oil (5.05 g) is obtained which for the most part consists of u, α-dichloro-4-trichloromethylacetophenone and contains small amounts of an unidentified product (HPLC: 76.2%).

/ T '

PDPI / T

HNMR 3 'δ 6.80 singlet (-C-CHCl ₂ )

δ 8.1 AA ¹ BB ¹ pattern (aromatic protons)

Part of the product is processed by gas-liquid chromatography * - graph separated using the column described in Example 12. The main fraction is determined by mass spectroscopy identified as a, a-dichloro-4-trichloromethylacetophenone

Example 21

+ 3

4-methylbenzophenone (3.26 g, 0.017 mol) and dichloromonoxide (5.77 g, 0.0664 mol) in carbon tetrachloride. (60 ml) are placed in a flask. The flask is closed and stored at room temperature for 5 days. The initial reaction is slightly exothermic and gradually a water phase separates out. The product is dried (MgSO.) And the solvent removed in a rotary evaporator. A viscous, pale yellow oil is obtained which crystallizes out on standing (8.22 g _r degree of purity according to HPLC 76.4%,

- 34 -

130048/0312

CR-7866

Yield TOO%). The product is made in carbon tetrachloride dissolved and filtered through a flat bed of Florisil. That Eluate is diluted with petroleum ether, cooled and filtered to remove traces of a low-melting solid (about 0.1 g) to separate. The solvent is removed from the filtrate, and light yellow crystals (3.42 g) are obtained. The Florisil bed is eluted with methylene chloride and the solvent is removed, to obtain an additional amount of lower purity product (2.19 g). The ones with carbon tetrachloride eluted fraction is sublimed (0.1 μ / 125-140 °) and off Carbon tetrachloride / petroleum ether recrystallized. You get pure 4-trichloromethylbenzophenone (melting point 110.7-111.5).

Elemental analysis for

56 C. 3, H 5, O Cl calculated 56 , 13 3, 03 34 35.50 found , 04 07 35.68

HNMR KBr

CDOL / T

: 3 '5 7.22-8.28 complex group (aromatic protons)

3.25μ (. == CH); - 6.07μ (conjugated. Ketone) 6.27μ, 6.34μ (aromatic C = C bond).

Example 22

+ 2

2 H ₂ O

- 35 -

130048/0312

(ftf.

CR-7866

5-nitroindane (1.14 g, 0.007 mol) and dichloromonoxide (2.42 g, 0.028 mol) in 25 ml of CCl- as described in Example 6 heated in a Carrius tube at 75 ° for 18.5 hours. The product is dried (MgSO ^) and the solvent in one Rotary evaporator removed. 1,1,3,3-tetrachloro-5-nitroindane is obtained in the form of a white, crystalline solid (2.10 g, purity according to HPLC 97.26%, yield 97.4%) ....- The Solid is combined with a similar sample and recrystallized from cyclohexane / petroleum ether and then sublimed (60 ° / 0.1μ). Essentially pure 1,1,3,3-tetrachloro-5-nitroindane is obtained (Melting point 69.5-70.5 °).

Elemental analysis for CgH ₅ NQ ₂ Cl-:

C. 92 1 H 4th N 47 Cl 0 calculated 35, 43 1 , 67 4th , 65 47 , 12 10.63 found 36, , 69 , 61 , 04.

PDPl / T ¹

HNMR 3 ^X 5 4.03 2H singlet (-CH ₂ -), δ 7.73-8.58 3H complex group (aromatic protons.)

Example 23

2-methylanthraquinone (5.89 g, 0.0265 mol) and dichloro monoxide (5.77 g, 0.0664 mol) in carbon tetrachloride (70 ml), as described in Example 6, heated to 75 ° C. in a Carrius tube for 20.25 hours. The product that comes in the form of a yellow, crystalline solid separates, is in methylene

- 36 -

130048/0312

CR-7866

dissolved chloride and filtered to separate a solid (0.49 g), which, based on the infrared spectrum, is assumed to be anthraquinone-2-carboxylic acid. The filtrate is dried (MgSCK) and the solvent removed in a rotary evaporator. 2-Trichloromethylanthraquinone is obtained in the form of a yellow, crystalline solid (8.49 g, degree of purity according to HPLC 94.26%, yield 92.5%). A portion of the product is made from carbon tetrachloride recrystallized and then sublimed (0.1μ). Pure 2-trichloromethylanthraquinone with a melting point is obtained from 157-158.2 °.

Elemental analysis for C ₁₅ H ₇ Cl ₃ O ₂ :

calculated
found

55.34 55.02

2.17 2.28

Cl

32.67
33.08

9.83 33.08

HNMR

KBr

CDCl / T

. 3 'δ 7.68-8.82 complex group (aromatic protons)

3.25 µ (= CH); 5.97 µ (conjugated ^ C = O bond);

6.28μ, 6.37μ (aromatic C = C bond), multiple bands

in the range 12.5μ (CCl ₃ ).

Mass spectrum;

measured
m / e calculated 9509 Assignment 3 23.9527 327, 9821 C ₁₅ H ₇ O ₂ Cl ₃ (mol ion) 288.9808 288, 0211 m-Cl 255.0194 255, C ₁₅ H ₈ O ₂ Cl

37 -

130048/0312

CR-7866

Example 24

Dichloro monoxide (4.41 g, 0.051 mol) in carbon tetrachloride (50 ml) is added to nitrofluorene (7.15 g, 0.034 mol) in carbon tetrachloride (50 ml) and the mixture is stirred at room temperature for 24 hours. The originally mild exothermic reaction leads to a homogeneous solution from which a solid precipitates. The reaction mixture is dissolved in methylene chloride, dried (MgSO ₄ ), and the solvent is then removed on a rotary evaporator. 9,9-K-dichloro-2-nitrofluorene (9.60 g, degree of purity according to HPLC 63.78 - '■ yield 64.63%) is obtained.

CDCl / T

HNMR 3 'δ 7.2-8.7 complex group (aromatic protons).

In summary, the invention relates to a method for α-Chlorination of side chains of electronegatively substituted ones aromatic compounds with dichloromonoxide.

End of description

- 38 -

130048/0312

Claims (9)

DR.-ING. WALTER ABITZ DR. DIETER F. MORP 'DIPL.-PHYS. M. GRITSCHNEDER Patent attorneys EGG. duPont de Nemours and Company : 2 σ. iiai ^: J58o Postal address PO Box 80010Ö. ΘΟΟΟ Munich 80 Pienzenauer Strasse 28 Telefcm 08 3823 Telegrams: Chemlndus Munich Telex: (O) 8 33093 CR-7866 Claims Process for the α-chlorination of a side chain of an aromatic compound, thereby known ζ e i h η e t that you can use dichloro monoxide with a aromatic compound represented by the following general formulas implements: CHR ¹ R "'(CR ¹ MR IVrV) ) _b (R'R "CH) _c 0 II III IV where in the general formula I: X stands for NO ₂ , CN, CF ₃ , Cl, Br, F, ,, SO ₃ R ₂ , 130048/0312 _ 1 - SO ₂ CF ₃ , SO ₂ Cl, SO ₃ NR ₃ R ₄ , OCR ₅ , N (R ₂ ) ₃ , OO , P (R ₂ J ₃ , Pj (OR ₂ J ₂ or CCl ₃ ; '0 Y stands for H, NO ₃ , Cl, Br, F, CN, CF ₃ , CR ₁ , SO ₂ R ₃ , O ■ ... SO ₃ R ₂ , SO ₂ NR ₃ R ₄ , OCF ₃ , OCR ₅ , ORg or aryl; Z represents H, Cl, or Br _; and in the general formulas II to V: ' X ¹ and X ² independently of one another represent NO ₂ , CN, CF ₃ , Cl, Br, F, CR ₁ , SO ₃ R ₂ , SO ₃ R ₂ , ■ O SO ₂ CF ₃ , SO ₂ Cl, SO ₂ NR ₃ R ₄ , OCR ₅ , N (R ₂ ) ₃ , 0 0 NRgCR ₂ , P (R ₂ J ₃ , P (OR ₂ J ₂ or CCl ₃ or in the general formula III also for hydrogen; Y ^ and Y ² stand independently of one another for 0 ■.-.- ■ H, NO ₂ , Cl, Br, CN or CR ₁ ; and in the general formulas I to V: R stands; for alkyl with 1 - 8 carbon atoms, aryl, Alkoxy of 1-4 carbon atoms, OH or NR ₃ R ₄ ; 2
R represents alkyl of 1-4 carbon atoms; 3 4
R and R independently of one another represent H or Alkyl of 1-4 carbon atoms; R stands for alkyl with 1-8 carbon atoms, trifluoro 130 0 4.8 / 0312 methyl or aryl; R stands for H or alkyl with 1 - 3 carbon atoms,
and R ¹ and R "independently of one another represent 'H, Alkyl with 1-3 carbon atoms or
together form a carbocyclic ring having 5-6 carbon atoms; and R "stands
also for alkyl with 1-20 carbon atoms; R "- ', R and R independently of one another represent H or Methyl; R and R independently of one another represent H, alkyl having 1-3 carbon atoms or together form a carbocyclic ring
5-6 carbon atoms; a is 0 or 1; - b and c are independently 1 or 2; η means 1 or 2; d means 0, 1 or 2, and m means a number from 0-6 / with the provisos that if X is NRgCOR ₂ , then Y and Z both cannot be H, and that if Y is OR ₆ , Z cannot be H. 2. The method according to claim 1, characterized in that in general formula I: X stands for NO ₂ , Cl, Br, CN, CF ₃ , CR ₁ , SO ₃ R ₂ , SO ₂ NR ₃ R ₄ , 0 0
SO ₃ R ₂ , OCR ₅ , NRgCR _2, or CCl ₃ ; O
Y stands for H, NO ₃ , Cl, Br, CN, CF ₃ , CR ₁ , SO ₃ R ₃ or Z represents H, Cl, or Br; and 130048/0312 in the general formulas II - V: ι 2
X and X stand independently for " Il NO ₂ , Cl, Br, CN, CF ₃ , CR ₁ , SO ₃ R ₂ , SO ₂ NR ₃ R ₄ , OO SO-, R ", OCRc r NR-XR.- or CCl, or mean in the general formula III also hydrogen; ■; .-, - ■ 1 2 Y and Y independently of one another represent H, NO ₂ , CL or B £; and 16 R -R, a, b, c, d, η and m have the meaning given in claim 1; and R ', R ", R and R independently of one another stand for Hydrogen or alkyl of 1-3 carbon atoms; and R " ¹ , R and R independently of one another represent hydrogen or methyl. 3. The method according to claim 2, characterized in that in the general formula I: 0 X is NO ₂ , Cl, Br, CN, CF ₃ ^ CR ₁ , SO ₂ R ₃ , SO ₃ NR ₃ R ₄ 0
or OCR ₅ ; Y represents H, NO ₃ , Cl or Br;
Z represents H, Cl, or Br; and
in the general formulas II-V: 130048/0312 12th
X and X stand independently of one another for Il NO ₂ , Cl, Br, CN, CP ₃ , CR ₁ , S ° ₂ ^R ₂ r ^SO 2 ^NR 3 ^R 4 O Il or OCRc or they mean in general Formula III also hydrogen; 12th Y and Y are independently H, NO ₂ , Cl or Br; and R ₁ represents alkyl with 1-8 carbon atoms, aryl or alkoxy with 1-4 carbon atoms; R ₂ represents alkyl of 1-4 carbon atoms; R ₃ and R- denote, independently of one another, alkyl having 1 to 4 carbon atoms; R ₅ represents alkyl having 1 to 8 carbon atoms or aryl; R ₆ represents alkyl having 1-3 carbon atoms; R ¹ , R ″, R and R independently of one another represent H or alkyl having 1-3 carbon atoms; R "', R and R independently of one another represent H or Methyl; a is 0 or 1; b and η mean 1 or 2, C-. is equal to 1; d is equal to Ö or 1; m means a number from 0 to 6 130048/0312 cR-7866 """." ■■. "* :; 30 ^ 9248 4. The method according to claim 3, characterized in that in general formula I: X stands for NO ₀ , Cl, CN, CF ₁ , CR 1 or SO ₀ R ₀ ; Y represents H, NO ₀ or Cl; . "■. Z represents H or Cl; R ₁ stands for alkyl with T - 8 carbon atoms, aryl or · alkoxy with 1-4 carbon atoms; R ₃ represents alkyl of 1-4 carbon atoms; R ¹ , R ″, R and R independently of one another represent H or alkyl having 1-3 carbon atoms; R "', R and R independently of one another mean H or Methyl; a is 0 or 1; with the proviso that X has the meaning of NO ₃ , Cl or CN when a = 1, Z = Cl and Y = NO ₀ or Cl. 5. The method according to claim 1, characterized in that the dichloro monoxide is present in the form of a gas in combination with a diluent gas. 6. The method according to claim 1, characterized in that the dichloromonoxide is present in the form of a solution. 7. The method according to claim 1, characterized in that in the tt-chlorination at least one α-hydrogen atom the aromatic compound is substituted. - O; - 1300Λ8 / 0312 8. The method according to claim 1, characterized in that in the case of α-chlorination, all of the -hydrogen atoms of aromatic compound can be substituted. 9. Process for the α-chlorination of a side chain of a electronegatively substituted aromatic compound, the net effect of the substituents being aromatic Ring is electron withdrawing, characterized in that dichloromonoxide is reacted with this aromatic compound. · 130048/0312