630-88-6

Basic information

• Product Name: FLUORESCEIN CHLORIDE
• Synonyms: FLUORESCEIN CHLORIDE;FLUORESCEIN DICHLORIDE;3',6'-DICHLOROFLUORAN;3',6'-DICHLOROFLUORANE;9’-[9h]xanthen]-3-one,3’,6’-dichloro-spiro[isobenzofuran-1(3h;3',6'-dichlorospiro(phthalide-3,9'-xanthene);2-(3,6-dichloro-9H-xanthen-9-yl)benzoic acid;Fluoresceinechloride
• CAS NO: 630-88-6
• Molecular Formula: C₂₀H₁₀Cl₂O₃
• Molecular Weight: 369.2
• EINECS: 211-147-7
• Mol File: 630-88-6.mol
• Article Data: 5

Chemical Properties

• Melting Point: 253-255 °C(lit.)
• Boiling Point: 485.02°C (rough estimate)
• Flash Point: 214.3ºC
• Appearance: white to light yellow crystalline powder.
• Density: 1.2569 (rough estimate)
• Refractive Index: 1.7360 (estimate)
• Solubility: almost transparency in hot Toluene
• CAS DataBase Reference: FLUORESCEIN CHLORIDE(CAS DataBase Reference)
• NIST Chemistry Reference: FLUORESCEIN CHLORIDE(630-88-6)
• EPA Substance Registry System: FLUORESCEIN CHLORIDE(630-88-6)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 37/39-26
• WGK Germany: 3
• Hazardous Substances Data: 630-88-6(Hazardous Substances Data)

Synthetic route

fluorescein (2321-07-5) → 3',6'-dichloro-spiro[phthalan-1,9'-xanthen]-3-one (630-88-6)

Conditions	Yield
With sulfolane; thionyl chloride In N,N-dimethyl-formamide at 60 - 80℃; for 2.5h; Temperature;	90.5%
With phosphorus pentachloride at 100℃;
With thionyl chloride
With phosphorus pentachloride In chlorobenzene at 140℃; for 6h;
With phosphorus pentachloride In chlorobenzene at 140℃; for 6h;

3-monochlorophenol (108-43-0) + 2-(4'-chloro-2'-hydroxybenzoyl)benzoic acid (76135-38-1) → 3',6'-dichloro-spiro[phthalan-1,9'-xanthen]-3-one (630-88-6)

Conditions	Yield
With zinc(II) chloride at 155 - 160℃; for 12h;	76%

phthalic anhydride (85-44-9) + 3-monochlorophenol (108-43-0) → 3',6'-dichloro-spiro[phthalan-1,9'-xanthen]-3-one (630-88-6)

Conditions	Yield
With ferric hydrogen sulphate at 160℃; for 13h; neat (no solvent);	70%
With zinc(II) chloride at 185 - 190℃;

phthalic anhydride (85-44-9) + activated aluminium → 3',6'-dichloro-spiro[phthalan-1,9'-xanthen]-3-one (630-88-6)

Conditions	Yield
Multi-step reaction with 2 steps 1: 195 - 200 °C 2: phosphorus pentachloride / 100 °C View Scheme

2-(2,4-dihydroxybenzoyl)benzoic acid (2513-33-9) → 3',6'-dichloro-spiro[phthalan-1,9'-xanthen]-3-one (630-88-6)

Conditions	Yield
Multi-step reaction with 2 steps 1: beim Erhitzen ueber den Schmelzpunkt 2: phosphorus pentachloride / 100 °C View Scheme
Multi-step reaction with 2 steps 2: phosphorus pentachloride / 100 °C View Scheme

recorcinol (108-46-3) + phenoldiazonium chloride-(4) → 3',6'-dichloro-spiro[phthalan-1,9'-xanthen]-3-one (630-88-6)

Conditions	Yield
Multi-step reaction with 2 steps 1: 195 - 200 °C 2: phosphorus pentachloride / 100 °C View Scheme
Multi-step reaction with 2 steps 2: phosphorus pentachloride / 100 °C View Scheme

3',6'-dichloro-spiro[phthalan-1,9'-xanthen]-3-one (630-88-6) → 3,6-dichloro-9-(carboxyphenyl)xanthen (87021-19-0)

Conditions	Yield
With acetic acid; zinc(II) chloride for 10h; Heating;	97%

N-(n-butyl)aniline (1126-78-9) + 3',6'-dichloro-spiro[phthalan-1,9'-xanthen]-3-one (630-88-6) → 3'-N-butylanilino-6'-chlorofluoran (915038-78-7)

Conditions	Yield
Stage #1: N-(n-butyl)aniline; 3',6'-dichloro-spiro[phthalan-1,9'-xanthen]-3-one; aluminum (III) chloride In sulfolane at 60 - 80℃; for 1.08333h; Stage #2: With hydrogenchloride; water In sulfolane at 0℃;	96%

ortho-ethylaniline (578-54-1) + 3',6'-dichloro-spiro[phthalan-1,9'-xanthen]-3-one (630-88-6) → 3,6-(o-ethylaniline)fluorescein

Conditions	Yield
With aluminum (III) chloride In N,N-dimethyl-formamide at 100 - 150℃; for 10.5h; Temperature; Reagent/catalyst;	86.2%

7-aza-bicyclo[2.2.1]heptane (279-40-3) + 3',6'-dichloro-spiro[phthalan-1,9'-xanthen]-3-one (630-88-6) → C32H30N2O3 (1225568-28-4)

Conditions	Yield
With zinc(II) oxide; zinc(II) chloride at 190℃; for 12h; high pressure reactor;	40%

3',6'-dichloro-spiro[phthalan-1,9'-xanthen]-3-one (630-88-6) + 4-(2-aminoethyl)benzenesulfonic acid → C36H30N2O9S2*H(1+)

Conditions	Yield
With zinc(II) chloride In sulfolane at 200℃; for 4h;	40%

1-methyl-piperazine (109-01-3) + 3',6'-dichloro-spiro[phthalan-1,9'-xanthen]-3-one (630-88-6) → 1-(9-(2-carboxyphenyl)-6-(4-methylpiperazine-1-yl)-3H-xanthene-3-ylidene)-4-methylpiperazine-1-ium chloride

Conditions	Yield
With zinc(II) chloride In 1,2-dichloro-benzene at 180℃; for 1h; Inert atmosphere;	14%

1,2,3,4-tetrahydroisoquinoline (635-46-1) + 3',6'-dichloro-spiro[phthalan-1,9'-xanthen]-3-one (630-88-6) → 3'-chloro-6'-(1,2,3,4-tetrahydroquinolin-1-yl)fluoran (915038-76-5)

Conditions	Yield
aluminum (III) chloride In sulfolane at 150℃; for 18h;	5.4%

3',6'-dichloro-spiro[phthalan-1,9'-xanthen]-3-one (630-88-6) → 3',6'-dichloro-spiro[isoindole-1,9'-xanthen]-3-one (10347-08-7)

Conditions	Yield
With ammonia

ethanol (64-17-5) + sodium acetate (127-09-3) + 3',6'-dichloro-spiro[phthalan-1,9'-xanthen]-3-one (630-88-6) + hydrochloride of diethylamine → 3.6-bis-diethylamino-fluorane

Conditions	Yield
at 200 - 220℃; im Autoklaven;

aniline hydrochloride (142-04-1) + 3',6'-dichloro-spiro[phthalan-1,9'-xanthen]-3-one (630-88-6) → 3.6-dianilino-fluorane

Conditions	Yield
at 220℃;

3',6'-dichloro-spiro[phthalan-1,9'-xanthen]-3-one (630-88-6) + (E)-3-Ureido-but-2-enoic acid ethyl ester (5435-44-9, 22243-66-9) + aniline (62-53-3) → 3.6-dianilino-fluorane

Conditions	Yield
at 210 - 220℃;
at 210 - 220℃;

3',6'-dichloro-spiro[phthalan-1,9'-xanthen]-3-one (630-88-6) + phosphorus pentasulfide → 3.6-dichloro-dithiofluorane

Conditions	Yield
at 185℃;

hydrogen iodide (10034-85-2) + 3',6'-dichloro-spiro[phthalan-1,9'-xanthen]-3-one (630-88-6) → 3.6-dichloro-hydrofluoranoic acid

Conditions	Yield
at 150℃; im Rohr;

water (7732-18-5) + 3',6'-dichloro-spiro[phthalan-1,9'-xanthen]-3-one (630-88-6) + aqueous-alcoholic NaOH-solution + zinc dust → 3.6-dichloro-hydrofluoranoic acid

ethanol (64-17-5) + potassium thiophenolate (3111-52-2) + 3',6'-dichloro-spiro[phthalan-1,9'-xanthen]-3-one (630-88-6) → 3.6-dithio-fluorescein-diphenyl ether

3',6'-dichloro-spiro[phthalan-1,9'-xanthen]-3-one (630-88-6) + alcoholic potassium hydrosulfide → 3.6-dithio-fluorescein

ammonia (7664-41-7) + 3',6'-dichloro-spiro[phthalan-1,9'-xanthen]-3-one (630-88-6) → 3',6'-dichloro-spiro[isoindole-1,9'-xanthen]-3-one (10347-08-7)

Conditions	Yield
at 190 - 200℃;

ammonium chloride + 3',6'-dichloro-spiro[phthalan-1,9'-xanthen]-3-one (630-88-6) + (E)-3-Ureido-but-2-enoic acid ethyl ester (5435-44-9, 22243-66-9) + lime/chalk/ → 3',6'-dichloro-spiro[isoindole-1,9'-xanthen]-3-one (10347-08-7)

Conditions	Yield
at 240 - 260℃;

aniline hydrochloride (142-04-1) + 3',6'-dichloro-spiro[phthalan-1,9'-xanthen]-3-one (630-88-6) + phenol (108-95-2) → 6-chloro-3-anilino-fluorane

ethanamine hydrochloride (557-66-4) + 3',6'-dichloro-spiro[phthalan-1,9'-xanthen]-3-one (630-88-6) + (E)-3-Ureido-but-2-enoic acid ethyl ester (5435-44-9, 22243-66-9) + zinc oxide → 6-chloro-3-ethylamino-fluorane

Conditions	Yield
at 160 - 170℃;

3',6'-dichloro-spiro[phthalan-1,9'-xanthen]-3-one (630-88-6) + sodium hydroxide → 2-(2,4-dihydroxybenzoyl)benzoic acid (2513-33-9) + benzoic acid (65-85-0) + recorcinol (108-46-3) + 2.4.2'.4'-tetraoxy-benzophenone

Conditions	Yield
at 230 - 240℃; Beim Schmelzen;

3',6'-dichloro-spiro[phthalan-1,9'-xanthen]-3-one (630-88-6) + lime milk → fluorescein (2321-07-5)

Conditions	Yield
at 230℃; unter Druck;

ethanol (64-17-5) + 3',6'-dichloro-spiro[phthalan-1,9'-xanthen]-3-one (630-88-6) + Na2S2 → compound C20H10O3S2

3',6'-dichloro-spiro[phthalan-1,9'-xanthen]-3-one (630-88-6) → Fast Acid Violet A 2 R

3',6'-dichloro-spiro[phthalan-1,9'-xanthen]-3-one (630-88-6) → Fast Acid Violet B

3',6'-dichloro-spiro[phthalan-1,9'-xanthen]-3-one (630-88-6) → oic acid rosamine A

3',6'-dichloro-spiro[phthalan-1,9'-xanthen]-3-one (630-88-6) → rhodamine B

Upstream product

• 108-46-3 recorcinol 
• 2513-33-9 2-(2,4-dihydroxybenzoyl)benzoic acid 
• 85-44-9 phthalic anhydride 
• 108-43-0 3-monochlorophenol 
• 76135-38-1 2-(4'-chloro-2'-hydroxybenzoyl)benzoic acid 
• 2321-07-5 fluorescein 

Downstream Products

• 87021-20-3 3',6'-dichlorohydrofluoran acid methyl ester 
• 915038-78-7 3'-N-butylanilino-6'-chlorofluoran 
• 104434-51-7 3',6'-Bis(2,5-dimethylanilino)fluoran 
• 2513-33-9 2-(2,4-dihydroxybenzoyl)benzoic acid 
• 65-85-0 benzoic acid 
• 108-46-3 recorcinol 
• 1225568-28-4 C₃₂H₃₀N₂O₃ 
• 2321-07-5 fluorescein 

Relevant articles and documents

A heat-sensitive printing fluoran dye preparation method (by machine translation)

The present invention relates to the field of heat-sensitive dye, in particular to a heat-sensitive printing fluoran dye preparation method. In order to fluorescein as the starting material, substitution, condensation, condensation to obtain the final product, 3 '- [octyl (2 - ethyl-phenyl) amino] - 6' - (2 - methyl phenyl) amino - spiro [isobenzofuran - 1 (3 H), 9' - [9 H] aroyl - 3 - one. Wherein fluorescein is fluorescein isothiocyanate, rhodamine or four for four ethyl base different thiocyanate rhodamine. The method of the invention simple and convenient operation, high conversion rate, low cost, easy to realize large-scale industrial production. This invention obtains the fluoran dye color rendering ability is strong, the Image reduction lifelike, clear, fast. The dye is applied to the non-ink printing new technologies, the technology through the dispersion coating, will include including C yellow, product, green three dye coating on paper, photographic paper is carried out by heating to obtain a high-quality Image. Because does not need to built-in cartridge, thereby producing very small size printer, can even built-in digital camera or camera in the mobile phone. (by machine translation)

Colorant compounds

Compounds of the formula wherein M is either (1) a metal ion having a positive charge of +y wherein y is an integer which is at least 2, said metal ion being capable of forming a compound with at least two chromogen moieties, or (2) a metal-containing moiety capable of forming a compound with at least two chromogen moieties, z is an integer representing the number of chromogen moieties associated with the metal and is at least 2, R1, R2, R3, R4, R5, R6, R7, a, b, c, d, Y, and z are as defined herein, Q? is a COO? group or a SO3— group, A is an organic anion, and CA is either a hydrogen atom or a cation associated with all but one of the Q? groups.

FLUORAN DERIVATIVES. PART IX. SYNTHESES OF HALOGENOFLUORANS

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