(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date WO 2016/038627 Al 17 March 2016 (17.03.2016) P O P C T

(51) International Patent Classification: (81) Designated States (unless otherwise indicated, for every C07D 317/46 (2006.01) kind of national protection available): AE, AG, AL, AM, AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, (21) International Application Number: BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, PCT/IN2015/000357 DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, (22) International Filing Date: HN, HR, HU, ID, IL, IN, IR, IS, JP, KE, KG, KN, KP, KR, 11 September 2015 ( 11.09.201 5) KZ, LA, LC, LK, LR, LS, LU, LY, MA, MD, ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, OM, (25) Filing Language: English PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA, SC, (26) Publication Language: English SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW. (30) Priority Data: 261 1/DEL/2014 11 September 2014 ( 11.09.2014) IN (84) Designated States (unless otherwise indicated, for every kind of regional protection available): ARIPO (BW, GH, (71) Applicant: SRF LIMITED [IN/IN]; Block- C, Sector-45, GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, ST, SZ, Unicrest Building, Gurgaon 122003, Haryana (IN). TZ, UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, TJ, TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, (72) Inventors: VARADHARAJ, Ganesan; SRF LIMITED, DK, EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, Block- C, Sector-45, Unicrest Building, Gurgaon 122003, LV, MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, Haryana (IN). POORNACHANDRAN, Ravichandran; SM, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, SRF LIMITED, Block- C, Sector-45, Unicrest Building, GW, KM, ML, MR, NE, SN, TD, TG). Gurgaon 122003, Haryana (IN). IYENGAR, Sarathy; SRF LIMITED, Block- C, Sector-45, Unicrest Building, Declarations under Rule 4.17 : Gurgaon 122003, Haryana (IN). PRASANNA, Kumar, — as to applicant's entitlement to apply for and be granted a Seetharaman; SRF LIMITED, Block- C, Sector-45, Uni patent (Rule 4.1 7(H)) crest Building, Gurgaon 122003, Haryana (IN). RAGURAMAN, Tiruchy, Srinivasan; SRF LIMITED, — of inventorship (Rule 4.17(iv)) Block- C, Sector-45, Unicrest Building, Gurgaon 122003, Published: Haryana (IN). GOMATHINAYAKAM, Anantharaman; Unicrest Building, Gurgaon 122003, Haryana (IN). — with international search report (Art. 21(3)) ANAND, Rajdeep; SRF LIMITED, Block- C, Sector-45, — before the expiration of the time limit for amending the Unicrest Building, Gurgaon 122003, Haryana (IN). claims and to be republished in the event of receipt of (74) Agent: SUNAINA KOUL; Lall Lahiri & Salhotra, RCY amendments (Rule 48.2(h)) House, C-235, Defence Colony, New Delhi 110024 (IN).

00 © v o

(54) Title: PROCESS FOR THE PREPARATION OF HALOGENATED DERIVATIVES OF AROMATIC ETHERS (57) Abstract: The present invention relates to the process for the preparation of halogenated derivatives of aromatic ethers. PROCESS FOR T PllEPAEATiON OF ATED DERIVATIVES OF AROMATIC ETHERS

FIELD OF THE INVENTION

The present invention relates to the process for the preparation of ha oge at d derivatives of aromatic ethers Formula

BACKGROUND OF THE INVENTION

The halogenated derivatives. f aromatic ethers of Fomiula I p a a important role as precursors tor the preparation of medicaments and crop protection agents.

Formula

wherein and R' together are an oxygen atom, arid X represents a hydrogen, fluorine, chlorine, or iodine.

The S Patent Mo. 7,148365 describes a process for the preparation of 5-bromo- 2,2-difi o be z -l 3-di xoles b reaction of 2,2 di or benz -dioxoies with bromine in the presence of at least two Friedel-Crafts catalysts of which one is hydrogen fluoride

The U.S Patent No. 4, 93,87 1 describes a process of preparation of 5-bromo-2,2- di uor ben o l ~diox les by reaction of .2,2-ditluorobeiizo- 3-diox es with bromine in the presence of carbon tetrachloride and iron powder.

The processes disclosed in the listed prior art employ either toxic solvents and or lewis acids, however, the yield of mono br o derivatives obtained torn such processes is substantially low Thus, there i a need in the art to provide simple. cost-effective and industrially scalable process for the preparation of compounds of Formula I.

SUMMARY OF THE INVENTION

The present invention provides a process for the preparation of compounds of Formula I, comprising;

a) reacting compound of Formula II with the source of bromine in the presence of hydrogen peroxide, and

Formula Π

wherein R and R' together are an oxygen atom, and X represents a hydrogen, fluorine, chlorine, bromine or iodine;

b) isolating compound of Formula I.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides a process for the preparation of compounds of Formula I, comprising;

a) reacting compound of Formula II with the source of bromine in the presence of hydrogen peroxide, and

Formula Π wherein I d R together are an oxygen atom, and X represents a hydrogen, fluo ne chlorine, bromine or iodine;

b) isolating compound of Formula

The compound of Formula 0 ay be prepared b any method known in the art, for example, method known .S Patent No. 4,895,871. The bromine source may be any alkali metal with mineral acid or yd ogen bromide. The alkali metal bromide may be selected from sodiu bromide, and bromide.The step a) may take place in the presence of mineral acid. The mineral acid ma be selected from hydrochloric acid, nitric acid, f i acid, phosphoric acid, hydrofluoric acidJltiorosulfouic aeid,chkm>sulfoT« ac d or mixture thereof. he step a) may e carried out in the presence or absence of organic solvent. The step a) may be carried at a temperature of about - ft C to about 0 C for example, at about 5 C to about . The step a) may h aided by stirring the contents. The step a) may take place for about 5 minutes to about 24 hours, for example, 10 minutes to about 60 hours, for example, 30 hours to about 50 hours.

The process for preparation of compound of Formula I may be carried in a continuous mode.

Th compound of Formula 1 is isolated fr om step a) reaction mixture. The compound of Formula I may be isolated by filtration, layer separation, decar atio evaporation, concentration, crys a!li atio and distillation or mixture thereof

While the present invention has been described in terms of its specific embodiments, certain modifications and equivalents will be apparent to those skilled in the art and are intended to be included within th scope of the present invention. EXAMPLE

Example 1

Process of preparation of 5-bromo-2, 2-difluoro-l, 3-benzodioxole:

A mixture of 2,2-difluoro-l, 3-benzodioxole (560 g) and (1100 g, Assay 47%) were taken in a reaction vessel fitted with cold condenser. The reaction mixture was cooled to 10°C and 30 % Hydrogen Peroxide solution (806 g) was added slowly in lot wise. Upon completion of addition, the temperature of the reaction mixture was cautiously raised to 70°C. The organic layer was separated and washed with 20 % of sodium metabisulfite and then washed with 20% of potassium bicarbonate solution. The organic layer was dried over magnesium sulfate and filtered. The filtrate was distilled under high vacuum to obtain the title compound.

Yield: 538 g W e claim:

1. A process for the preparation of compounds of Formula I, comprising;

a) reacting compound of Formula II with the source of bromine in the presence of hydrogen peroxide, and

Formula II

Formula I

wherein R and R' together are an oxygen atom, and X represents a hydrogen, fluorine, chlorine, bromine or iodine;

b) isolating compound of Formula I.

2. The process of claim 1, wherein bromine source of step a) is any alkali metal bromide with mineral acid or hydrogen bromide.

3. The process of claim 2, wherein alkali metal bromide is selected from , potassium bromide and caesium bromide.

4. The process of claim 2, wherein mineral acid is selected from hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, fluoro sulfonic acid, chloro sulfonic acid or mixture thereof.

5. The process of claim 1, wherein step a) is carried at a temperature of about - 15°C to about 100°C.

6. The process of claim 1, wherein compound of Formula I is isolated by filtration, layer separation, decantation, evaporation, concentration, crystallization and distillation or mixture thereof. A . CLASSIFICATION O F SUBJECT MATTER INV. C07D317/46 ADD.

According to International Patent Classification (IPC) o r t o both national classification and IPC

B . FIELDS SEARCHED Minimum documentation searched (classification system followed by classification symbols) C07D

Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched

Electronic data base consulted during the international search (name of data base and, where practicable, search terms used)

EPO-Internal , CHEM ABS Data

C . DOCUMENTS CONSIDERED T O B E RELEVANT

Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.

EP 1 595 877 Al ( LANXESS DEUTSCHLAND GMBH 1-6 [DE] ) 16 November 2005 (2005-11-16) exampl es 1, 2

J . GORECKA ET.AL. : 1-6 "Deprotonati on-tri ggered heavy hal ogen mi grati ons as a key t o the structural el aborati on of 2 ,2-di f l uoro-l ,3-benzodi oxol e" , EUR. J . ORG. CHEM. , 2004, pages 64-68, XP002752802 , page 64, r i ght col umn , scheme

US 5 633 218 A (SPEDDING DONNA L [US] ET 1-6 AL) 27 May 1997 (1997-05-27) exampl e 2 -/-

X| Further documents are listed in the continuation of Box C . See patent family annex.

* Special categories of cited documents : "T" later document published after the international filing date o r priority date and not in conflict with the application but cited to understand "A" document defining the general state of the art which is not considered the principle o r theory underlying the invention to be of particular relevance "E" earlier application o r patent but published o n o r after the international "X" document of particular relevance; the claimed invention cannot be filing date considered novel o r cannot b e considered to involve a n inventive "L" documentwhich may throw doubts o n priority claim(s) orwhich is step when the document is taken alone cited to establish the publication date of another citation o r other "Y" document of particular relevance; the claimed invention cannot be special reason (as specified) considered to involve a n inventive step when the document is "O" document referring to a n oral disclosure, use, exhibition o r other combined with one o r more other such documents, such combination means being obvious to a person skilled in the art "P" document published prior to the international filing date but later than the priority date claimed "&" document member of the same patent family

Date of the actual completion of the international search Date of mailing of the international search report

11 January 2016 26/01/2016

Name and mailing address of the ISA/ Authorized officer European Patent Office, P.B. 5818 Patentlaan 2 N L - 2280 HV Rijswijk Tel. (+31-70) 340-2040, Fax: (+31-70) 340-3016 Kl ei derni gg, Ol i ver C(Continuation). DOCUMENTS CONSIDERED TO BE RELEVANT

Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.

CH 676 119 A5 (CIBA GEIGY AG) 1-6 14 December 1990 (1990-12-14) example 1 Patent document Publication Patent family Publication cited in search report date member(s) date

EP 1595877 Al 16-11-2005 AT 425156 T 15-03-2009 CN 1696125 A 16-11-2005 DE 102004024012 Al 01-12-2005 EP 1595877 Al 16-11-2005 P 4828862 B2 30-11-2011 P 2005325116 A 24-11-2005 US 2005272942 Al 08-12-2005

US 5633218 A 27-05-1997 NONE

CH 676119 A5 14-12-1990 NONE