DD227136A1 - PROCESS FOR THE PREPARATION OF NEW BENZO-1,3,2-OXATHIAPHOSPHOLENES - Google Patents

Abstract

The invention relates to a process for the preparation of novel benzo-1,3,2-oxathiaphospholenen of the general formula I in which R is hydrogen, alkyl, aryl, alkoxy; R 1 represents halogen, alkoxy, phenoxy, phenylthio, optionally mono- or polysubstituted on the phenyl nucleus by halogen or donors, amino, optionally monosubstituted or disubstituted by alkyl or aryl; n stands for 1 or 2 and m stands for 1 or 3. The aim of the invention is to produce new benzo-1,3,2-oxathiaphospholene in a simple manner. According to the invention benzene-1ol-2-thiols are reacted with phosphorus halides to benzo-1,3,2-oxathiaphosphorhalogeniden, from which benzo-1,3,2-oxathiaphospholene be obtained with alcohols, phenols, thiophenol, primary or secondary amines. These compounds can be used as intermediates for crop protection products, for the detergent industry and as flame retardants.

Description

Title of the invention

Process for the production of new ones. Benzo - 1, 3, 2 - oxathiaphospholenes

Fields of application of the invention

The invention relates to a process for the preparation of novel benzo - 1, 3 »2 - oxathiaphospholenes of general formula I.

in which

R is hydrogen, alkyl, aryl, alkoxy;

R is halogen, alkoxy, phenoxy, phenylthio, optionally on phenyl nucleus. monosubstituted or polysubstituted by halogen or donors, an amino group, optionally substituted by alkyl or aryl, once or twice;

η is 1 or 2;

m. stands for 1 or 3, which are important as inorganic intermediates for crop protection agents, for the detergent industry and as flame retardants.

-R 8.84-Ο19ΟΟ35

- 2 characteristic of the known technical. solutions

Benzo - 1 "3 * 2 - diaxaphospholenes and / or benzo - 1" 3 "2 - dithiaphospholenes are obtained by known methods, in that phosphorus and halogenides are reacted with; Catechol or "o-Benzendithiolen implemented; become.

(L- _AFSCHÜTZ; W. BROEEER; Ber * dtsch. ". Former Ges * 61 (1928) 1264; D '.. B * DEWIiEY ,, DZ · ΠΕΗΒΕΪ *" L ..- T · LIU " Phosphorus and Sulfur-12 (1982) 243, Pat, US Pat. No. 3,632,690 (1967)) Substituted benzo-2-chloro-1 * -3 »2-oxathiaphospholenes are prepared by known methods by reacting substituted o-meraaptophenol with hairpourri.chorid. (Pat., USA, No. 3661841 (1972)) hairpiece of this process is "that the reaction temperature is limited to 307.8 K by the solvent of diethyl ether, and the reaction thereby becomes 13 to takes 14 hours * ¹ Uachteil the known method _is, that benzo; -. 1 "3" · 2 - oxathiaphospholene of general formula I thus not accessible...

Aim of the invention

The aim of the invention is the preparation of novel benzo - Λ » 3" 2 - · oxathiaphospholenes in a simple manner

Presentation of the nature of. invention

The object of the invention is a process for producing these compounds *

According to the invention, new benzo-1,3 '2-o-xaphthaphospholenes of the general formula are obtained. I get, by adding Benz - 1 oil. - 2 thiols of the general formula. II "in the. · R the same. Meaning, as in formula. I * has with phosphorus halides to benzo - 1 _r 3 * 2 - axathiaphosphor halides (III) or * (V), dsr general For, - meH _Ia; in the. X to be converted for halogen. those with. Alcohols, .. Phenols * Ehiophenol "primary or secondary. Amines in an anhydrous organic solvent »

like ζ. Β »Benzen, in the presence of proton acceptors the benzo - 1» 3 »-. 2 - oxathiapho.spholene of the general formula Ib _r in which H has the meaning as in formula I except halogen has to be kept.

The.; inventive method is illustrated by equation 1 »

Application Examples Example 1

To 12 _r 2 g. (88.5 mmol) of phosphorus trichloride are 7.4 g (59 mmol) of o-mercaptophenol. Slowly, while stirring, drip t »The evolving hydrogen chloride is expelled in an argon stream. It will, as long as the reflux condenser. heated to boiling until the Ghlorwasaerstoffentwicklung is complete »is then in vacuo, distilled ·. The 2 - chlorine. - benzo - 1 , 3 ,, 2 - oxathiaphospholen goes on. _133; 3 Pa from 348 to 349 K as a colorless liquid. The compound is readily soluble in the most common organic solvents such as, for example, benzene, methanol, methylene chloride, THF.

Yield 4.5 g. = _48; $ 5 theory (based on

o.-Hercaptophenol)

Molecular formula. Cg.H.OSPGl. Mol "wt" i90 _r 6

Example. X

2 - phenolthio - benzo. - 1 _£ 3 »; _ 2 • r.

6> mmol) of thiophenol and 3 »2 g (31» .6 mmol} of triethylamine are dissolved in benzene, - dropwise, while stirring, stirring 7 ^ 4 S (31, ϊβ mmol), 2 -Brom - benzo - 1 "3" 2 -?.. oxathiaphospholen _r also dissolved in benzene "professional completion of the reac tion is the trieth ^ laminhydrobromid filtered" distilled solvent and DAS DER residue, vacuum distilled ..

Daa 2 - phenolthio - benzo .. - 1 "3"> 2 - ~ oxathiaphospholen distilled, at 26, 6: Pa from 430 - 432; K as colorless. Liquid; over .. The compound is in the gebräuciiliciien organic solvents "such as benzene beispiellaweis.ej _r Metiianol · ,, meth ^ lencnlorid. and TEP good; soluble.-

Yield 3 _,? 9g = 46>_; , 8: fo of the ¹ theory empirical formula. C ₁₂ H ₂ OS ₂ P MoI ^ W x 264,: 3-

Claims (1)

- 5 invention claim Process: for the production of new ones. Benzo - 1, 3 χ 2 - oxathia - phospholenes of the general formula I where R is hydrogen,. Alkyll, _aryl; , alkoxy; R is halogen, alkoxy, phenoxy,., Optionally; one on the phenyl nucleus by halogen or donors or multiple _r · an amino group "optionally substituted by alkyl Ojder aryl mono- or: two polysubstituted; η is -1 or 2; m is T. X 3 is or "* characterized" in that Benz - 1 Oil - 2:.... thiols of the general formula II · ".. in: DER R has the same meaning as in formula I has _r Benzo-1, 3 ", 2-oxathiaphosphorus (III) or (Y) halides of the general formula Ia" in the formula. X for: - Halogen, s.tsht be repositioned, from which, with alcohols, phenols, thieophenol, primary or secondary amines in a water-free organic solvent, in the presence of proton acceptors, the benzoic, 1,3,3-oxathiaphospholenes of general formula Ib in the R ¹ the]
become.· R has the meaning as in Formal I except halogen, has received 1 SeSia drawing