Two Outside, One Inside

No. This is a rescue, and rescue in a potentially IDLH atmosphere is not an awareness-level action.

• You have turnout gear, SCBA, and no chemical-protective suit. Turnout gear is not chemical protection against a solvent, and the two people outside are already symptomatic, which suggests meaningful concentrations at low elevation - the worker on the floor is at the worst place in the room, where the vapor is heaviest and oxygen may be displaced.
• What you can do without entering: shout clear self-evacuation instructions through the open door, and open that roll-up door fully from outside to improve ventilation - an exterior door operation is not entry. If he responds and can move, talk him out along the wall to the doorway. If he does not respond, the IC decides whether a rescue attempt is justified with the right ensemble and backup; your request goes up immediately as a rescue, not a spill.
• Do not use 'protect in place' as the plan. For a solvent vapor in a small slab building, telling an unresponsive or impaired person to stay put buys nothing. If a real rescue cannot be mounted in time, the IC needs to know that and make a deliberate call.
• Keep your crew out of the doorway, out of the plume, and upwind, and set the perimeter to keep everyone else out of the building.

Decon happens before the hot zone, before transport, and before either patient gets near your apparatus.

• Location: upwind and, where possible, on higher ground, between the exclusion zone and the ambulance staging area, on a tarp or over a berm so runoff does not reach a storm drain. Same side of the door as the wind, not across the plume.
• The patients: direct them into the area themselves. Outer clothing and jewelry off, cut rather than pulled over the head where clothing is wet, double-bagged. Copious water and mild soap; flush eyes for a full 15 minutes if there is irritation; then wrap in blankets and keep them warm. Document what was removed and when.
• Contain the runoff - a solvent sheen reaching a storm drain turns a two-patient incident into a waterway notification.
• Do not let them into the ambulance cab, the patient compartment, or your engine cab until gross decon is done. Tell the arriving EMS crew what the product is, that the patients are deconned, and that they were symptomatic (burning skin, dizziness, vomiting).
• Assisting ambulatory patients with hand-holding and routing is within reach; anything requiring you to work in the contaminated area, or to handle a patient who cannot assist, is a hazmat-team or EMS task. Minimum gloves and eye protection for anyone touching a potentially contaminated patient.

It changes the fire question, not the health question.

• A flash point near 140F puts the product at the boundary of combustible liquid classifications, and at 34F ambient it will not be giving off much flammable vapor on its own. But a flash point near 140F is right on a classification line, and owners routinely round, misremember, or quote the wrong product. It is a reported value, not a measured one.
• It does not explain your patients. A liquid that is barely volatile at 34F does not normally produce dizziness and vomiting in someone standing in the room, unless: the tank headspace was released under pressure when the seam split, the product contains a more volatile or more toxic component than the owner knows, the room has poor ventilation and the concentration built up over time, or the symptoms are not from inhalation at all.
• So it does not justify a closer approach or a relaxed perimeter. It is also a reminder that low flammability is not low hazard - and that a person down inside a small, poorly ventilated slab building may be short of oxygen regardless of the product.
• Report the discrepancy to the hazmat team as an open question: the reported flash point and the patient presentation do not match, so they should treat the atmosphere as unknown and meter before entry.